JP4753685B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

  The present invention relates to a toner for developing electrostatic images using a polyester resin useful as a binder for dry toners used for developing electrostatic images or magnetic latent images in electrophotography, electrostatic recording, electrostatic printing, and the like. The present invention relates to a carrier using the toner, a developer, an image forming method using the toner, and an image forming apparatus.

  Conventionally, it is known to use a polyester resin as a binder for the purpose of improving the low-temperature fixing performance of the toner (Patent Documents 1, 2, etc.). However, in order to further improve the low-temperature fixability of the toner, it is necessary to lower the molecular weight and glass transition temperature (hereinafter abbreviated as Tg), but in such a case, the toner has poor blocking resistance under high temperature and high humidity. Had problems. Further, when such a resin is used, there is a problem that the toner component adheres to the carrier or the developing sleeve and the charging ability of the developer is lowered. Furthermore, it has been found that such a decrease in charging ability becomes significant only over time in a high-temperature and high-humidity environment or a low-temperature and low-humidity environment, and also under a high image area output. There has been a demand for a toner and an image forming apparatus that can stably output a high-quality image in any usage environment in a wider range of usage environments of a user even if there is no particular problem in a normal usage environment.

  In addition, it has been conventionally known that a charge control agent (charge control agent) is contained in a binder for the purpose of improving the chargeability and charge stability of the toner and preventing scumming (Patent Document 3). However, the charge control agent has a lower low-temperature fixing performance than the polyester resin, and has a function of inhibiting the low-temperature fixing performance of the polyester resin when present in the toner. Therefore, in order to further improve the low-temperature fixability of the toner, it is necessary to uniformly disperse the charge control agent in the toner and to exhibit sufficient charging performance with a smaller amount.

  In the developing process, a developer used in electrophotography, electrostatic recording, electrostatic printing, and the like is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then in a transfer process. After being transferred from the photoreceptor to a transfer medium such as transfer paper, it is fixed on the paper surface in a fixing step. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, Non-magnetic toners are known. In the two-component development method, the developer deteriorates due to the toner particles adhering to the carrier surface, and since only the toner is consumed, the toner concentration in the developer decreases, so the mixing ratio with the carrier is kept constant. Therefore, the developing device is relatively large. On the other hand, in the one-component development method, the size of the apparatus has been further reduced due to the higher functionality of the developing roller and the like.

  In recent years, office automation and colorization have further progressed in offices, and not only copying originals consisting only of conventional characters, but also pictorials read from graphs created with personal computers, images taken with digital cameras, scanners, etc. Opportunities to output manuscripts with printers and make many copies as presentation materials are increasing. The printer output image has a complicated structure mixed in one original such as a solid image, a line image, and a halftone image, and various demands are increasing along with a demand for high reliability of the image.

  Conventional electrophotographic processes using a one-component developer are classified into a magnetic one-component developing method using magnetic toner and a non-magnetic one-component developing method using non-magnetic toner. In the magnetic one-component development method, a developer carrying member provided with a magnetic field generating means such as a magnet is used to hold a magnetic toner containing a magnetic material such as magnetite, and a thin layer is developed by a layer thickness regulating member. Recently, a large number of small printers have been put into practical use. However, the magnetic material has a disadvantage that it is colored, and many are black and difficult to color.

  In contrast, in the non-magnetic one-component development method, since the toner does not have a magnetic force, a toner replenishing roller or the like is pressed against the developer carrying member to supply the toner onto the developer carrying member and electrostatically hold the layer. The film is developed with a thin layer by a thickness regulating member. This has the advantage that it does not contain a colored magnetic material, so it can be used for colorization. Furthermore, since no magnet is used for the developer carrier, the device can be further reduced in weight and cost. It has been put to practical use.

  On the other hand, in the two-component development method, a carrier is used as a means for charging and transporting toner, and the toner and the carrier are sufficiently stirred and mixed in the developing device, and then transported to the developer carrying member for development. Even in use, it is possible to maintain stable chargeability and transportability, and it is easy to cope with high-speed developing devices.

Compared to this, there are still many problems to be improved in the one-component development method. In the one-component development system, since there is no stable charging or conveying means like a carrier, charging failure and conveyance failure are likely to occur due to long-term use and high speed. That is, in the one-component development method, after the toner is transported onto the developer carrier, the toner is thinned by the layer thickness regulating member and developed, but the friction between the toner and the developer carrier, the layer thickness regulating member, etc. Since the contact time with the charging member and the frictional charging time are very short, the amount of low-charged and reverse-charged toner tends to increase more than the two-component development method using a carrier.
In particular, in the non-magnetic one-component developing method, the toner (developer) is usually transported by at least one toner transport member, and the electrostatic latent image formed on the latent image carrier is developed by the transported toner. In this case, the thickness of the toner layer on the surface of the toner conveying member must be as thin as possible. This is also true when a two-component developer with a very small carrier is used, and particularly when a one-component developer is used and the toner has a high electrical resistance. Since the toner needs to be charged by the developing device, the toner layer thickness must be remarkably reduced. This is because if the toner layer is thick, only the surface of the toner layer is charged, and the entire toner layer is difficult to be uniformly charged. For this reason, the toner is required to maintain a faster charging speed and an appropriate charge amount.

Therefore, a charge control agent or an additive is conventionally added to stabilize the charge of the toner. The charge control agent functions to control the triboelectric charge amount of the toner and maintain the triboelectric charge amount. Typical negative charge control agents include monoazo dyes, salicylic acid, naphthoic acid, dicarboxylic acid metal salts / metal complex salts, diazo compounds, complex compounds with boron, etc. Examples of the charge control agent include quaternary ammonium salt compounds, imidazole compounds, nigrosine, and azine dyes.
However, some of these charge control agents have a chromatic color, and many cannot be used for color toners. In addition, some of these charge control agents are poorly compatible with the binder resin, so that those present on the surface of the toner that are greatly involved in charging are likely to be detached, resulting in variations in toner charging. There is a drawback that the developing sleeve is easily contaminated and the photosensitive member filming is likely to occur.

  For this reason, in the prior art, a good image can be obtained in the initial stage, but the image quality gradually changes, causing a phenomenon that background stains and blurring occur. In particular, when applied to color copying and continuously used while replenishing toner, the amount of toner charge is reduced, resulting in an image that differs significantly from the color tone of the initial copied image, and it cannot withstand long-term use. The image forming unit called a process cartridge has to be replaced at an early stage only by copying to a certain extent. For this reason, the load on the environment is large, and it takes time and effort for the user. Furthermore, since many of these cartridges contain heavy metals such as chrome, they have recently become a problem from the viewpoint of safety.

  In order to solve the above problems, resin charge control agents having improved compatibility with binder resins, transparency of toner fixed images, and safety are known. Since these resin charge control agents have good compatibility with the binder resin, they are excellent in stable chargeability and transparency. However, these resin charge control agents have the disadvantage that the charge amount and charging speed are inferior compared with toners using metal salts and metal complex salts of monoazo dyes, salicylic acid, naphthoic acid and dicarboxylic acid. In addition, the chargeability is improved by increasing the amount of the resin charge control agent added, but the toner fixability (low temperature fixability, offset resistance) is adversely affected. Furthermore, these compounds have high environmental stability (humidity resistance) of the charge amount. For this reason, there is a problem that soiling (fogging) is likely to occur. (For example, see Patent Documents 4 to 7)

  Therefore, a copolymer of a monomer containing an organic acid salt such as a sulfonate group and an aromatic monomer having an electron withdrawing group has been proposed. However, a sufficient amount of charge is secured by the hygroscopicity and adhesiveness that are thought to be due to monomers containing organic acid salts such as sulfonate groups, but the dispersion in the binder resin is not sufficient, and the toner is charged for a long time. The effect of suppressing variation in the thickness and preventing filming on the developing sleeve and the photoreceptor are not sufficient. (For example, see Patent Documents 8 to 11)

  Furthermore, in order to further improve the compatibility with styrene resins and polyester resins as binder resins, monomers containing organic acid salts such as sulfonate groups, aromatic monomers having electron-withdrawing groups, styrene monomers and polyesters, respectively. Copolymers with system monomers have also been proposed, but the effect of maintaining the charge amount over a long period of time and the effect of preventing the development sleeve and the photoreceptor filming are not sufficient. In particular, as a binder resin for a full color toner, it is insufficient for a suitable polyester resin or polyol resin in terms of color developability and image strength.

  In recent years, the demand for printers has expanded, and the size, speed, and cost of the devices have been increasing. As a result, higher reliability and longer life have been demanded for the devices. However, with these resin charge control agents, the charge control effect cannot be maintained, and the developing sleeve and the layer thickness regulating member (blade and roller) are contaminated, so that the charging performance of the toner is reduced, and the photoconductor filming is performed. There was a problem.

  In addition, a process that develops in a short time with a small amount of developer due to downsizing and speeding up, and a developer having better charge rising property is required. Regarding development, various development methods have been proposed for both two-component and one-component developers, but it is excellent in that it can be reduced in size and weight, and non-magnetic one-component development that eliminates the need for a carrier is used for printers Is suitable. In this development system, the toner replenishment property to the developing roller and the toner retaining property of the developing roller are poor, so the toner is forcibly rubbed against the developing roller, or the amount of toner on the developing roller is regulated by a blade. As a result, the toner tends to film on the developing roller, resulting in a problem that the life of the developing roller is shortened and the charge amount of the toner becomes unstable. This also prevents good development. Therefore, in color toners for non-magnetic one-component development, in addition to the properties required for general color toners, the heat resistance of the binder resin used for the toner is often inferior, and the toner on the developing roller is often inferior. Filming is likely to occur.

However, the above-described prior art has the disadvantage that the charge amount and the charge speed are inferior in the examples described in Patent Documents 1 to 4, and in order to prevent this, the chargeability is improved by increasing the addition amount of the resin charge control agent. However, it adversely affects toner fixability (low temperature fixability, offset resistance). Furthermore, these compounds have a large environmental stability (humidity resistance) of the charge amount, but there is also a problem that background contamination (fogging) tends to occur.
In the examples of Patent Documents 8 to 11, a sufficient charge amount is ensured by hygroscopicity and adhesiveness, but the dispersion to the binder resin is not sufficient. There is a problem that the effect of preventing ming is not sufficient.

Japanese Patent Laid-Open No. 62-178278 JP-A-4-313760 JP-A-7-062766 JP-A 63-88564 JP 63-184762 A JP-A-3-56974 JP-A-6-230609 JP-A-8-30017 JP-A-9-171271 JP-A-9-21896 JP 11-218965 A

The present invention is excellent in both blocking resistance and low-temperature fixability of toner under high temperature and high humidity, does not cause scumming, and is used in a high-temperature and high-humidity environment or a low-temperature and low-humidity environment. High quality images with any use even under time, that is, electrostatic charge that can stably output high images without problems such as toner component adhering to the carrier or developing sleeve and reducing the charging ability of the developer An object is to provide a toner for image development.
In addition, the present invention can stably control and maintain the triboelectric charge amount of the toner, can maintain a stable triboelectric charge property with little environmental fluctuation, and can convey toner, developability, and transfer. An object of the present invention is to provide a toner for developing a dry electrostatic image, which has excellent properties and storability and does not generate an abnormal image due to adhesion to a photoreceptor.
Another object of the present invention is to provide a one-component developer, a two-component developer using the toner for developing an electrostatic charge image, a carrier used therefor, an image forming method using the developer, and an image forming apparatus. And

  As a result of intensive studies to solve these problems, the present inventors have used a toner binder made of a polycondensation polyester resin formed in the presence of a specific catalyst, and the toner particle size is defined as a prescribed particle size. The inventors have found that the problem can be solved for the first time by controlling the particle size distribution or using a specific charge control agent, and have completed the present invention.

That is, the present invention is solved by the following (1) to (3).
(1) In the method for producing an electrostatic charge image developing toner containing at least a colorant and a binder resin, the toner has a volume average particle diameter of 2.0 to 10.0 μm and a volume average particle diameter (Dv) The ratio (Dv / Dn) to the number average particle diameter (Dn) is in the range of 1.00 to 1.40, and the binder resin contains at least a polycondensation polyester resin. And a method for producing a toner for developing an electrostatic image, wherein the toner is formed in the presence of titanium dihydroxybis (triethanolaminate ) .

(2) “The toner contains a charge control agent, and the charge control agent is represented by any one of the following general formulas (III) to (V), (VIII), (IX), bis [1- (5-chloro-2-hydroxyphenylazo) -2-naphtholato] chromium (III) acid, nigrosine, perfluoroalkyltrimethylammonium iodide, polyhydroxyalkanoate, or a monomer represented by (VI) and (VII) The method for producing a toner for developing an electrostatic charge image according to (1) above, wherein the monomer represented by (1) is one or more selected from copolymers obtained by polymerization at a predetermined ratio;

（Ｒ_１は水素原子又はメチル基、Ｒ_２は水素原子又はメチル基であり、Ｒ_３はアルキレン基であり、Ｒ_４、Ｒ_５及びＲ_６は各々アルキル基である。）

(R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group, and R ₄ , R ₅ and R ₆ are each an alkyl group.)

（式中、ａ_１は０．８〜０．９８であり、ｂ_１は０．０１〜０．１９であり、ｃ_１は０．０１〜０．１９であり、ａ_１＋ｂ_１＋ｃ_１は１である。）
（３）「前記トナーが帯電制御剤を含有し、該帯電制御剤が樹脂帯電制御剤からなり、該樹脂帯電制御剤が単量体として少なくとも（１）スルホン酸塩基含有モノマー、（２）電子吸引基を有する芳香族モノマー、（３）アクリル酸エステルモノマー及び／またはメタアクリル酸エステルモノマー、（４）芳香族ビニルモノマーのうち、（１）〜（３）または（１）〜（４）を構成単位とし、該樹脂帯電制御剤の体積抵抗が９．５〜１１．５ＬｏｇΩ・ｃｍであり、該樹脂帯電制御剤において重量平均分子量１×１０^３以下の成分の含有割合が１０重量％以下であることを特徴とする前記（１）に記載の静電荷像現像用トナーの製造方法」。

(Wherein, a ₁ is 0.8 to 0.98, b ₁ is 0.01 to 0.19, c ₁ is 0.01 to 0.19, and a ₁ + b ₁ + c ₁ is 1)
(3) “The toner contains a charge control agent, the charge control agent comprises a resin charge control agent, and the resin charge control agent is at least (1) a sulfonate group-containing monomer as a monomer, and (2) an electron. (1) to (3) or (1) to (4) among aromatic monomers having an attractive group, (3) acrylic acid ester monomers and / or methacrylic acid ester monomers, and (4) aromatic vinyl monomers. As a constituent unit, the volume resistance of the resin charge control agent is 9.5 to 11.5 Log Ω · cm, and the content ratio of the component having a weight average molecular weight of 1 × 10 ³ or less in the resin charge control agent is 10% by weight or less. The method for producing a toner for developing an electrostatic charge image according to the above (1), which is characterized in that it exists.

The volume average particle diameter of the present invention is 2.0 to 10.0 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.00 to 1.40. The toner for developing electrostatic images using a toner binder resin composed of a polycondensation polyester resin is excellent in both blocking resistance and low-temperature fixability under high temperature and high humidity, and in a high temperature and high humidity environment or at a low temperature. Under any low humidity environment, even under high image area output, there is no problem such as deterioration of the charging ability of the developer by fixing the toner component to the carrier or the developing sleeve, regardless of how it is used over time. It is a toner that can stably output a high image, and has good storage stability, melt flowability, and charging characteristics. Moreover, even if it does not use the tin compound which has an environmental problem as a catalyst, it has favorable resin performance.
Further, a toner containing the above-mentioned toner of the present invention further containing a charge control agent, particularly the specific charge control agent, does not generate scumming under high temperature and high humidity, has good chargeability, and has little fluctuation in charging environment. In addition, since it contains a toner binder that has a function excellent in low-temperature fixability and does not use a biotoxic and environmentally problematic tin compound as a catalyst, a low environmental load is achieved.
Further, the toner for developing an electrostatic charge image using a resin charge control agent having a specific component and a component ratio with respect to a polyester resin formed in the presence of a specific titanium-containing catalyst as the binder resin for the toner of the present invention. Has a high charge amount and a sharp charge amount distribution, has good charge rise, is excellent in background stains, is not affected by changes in the greenhouse temperature, and has a development carrier (development roller or sleeve) over a long period of tens of thousands of sheets. ) And developing layer thickness regulating members (blades and rollers) and photoconductor filming, excellent crushability, high productivity, and excellent electrostatic charge image developing toner with no environmental problems Especially suitable for full color use.
Furthermore, the present invention can provide a dry one-component developer, a two-component developer, and an image forming method and an image forming apparatus using the toner.

Hereinafter, the present invention will be described in detail.
The titanium-containing catalyst (a) used in the present invention is a compound represented by the formula (I) or (II), and two or more kinds may be used in combination.
In the general formulas (I) and (II), X is a residue obtained by removing the H atom of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms. The total number of secondary and tertiary amino groups is usually 1 to 2, preferably 1.
Examples of the monoalkanolamine include ethanolamine and propanolamine. Polyalkanolamines include dialkanolamines (such as diethanolamine, N-methyldiethanolamine, and N-butyldiethanolamine), trialkanolamines (such as triethanolamine, and tripropanolamine), and tetraalkanolamines (N, N, N). ', N'-tetrahydroxyethylethylenediamine and the like).

  In the case of polyalkanolamine, at least one OH group is present in addition to the OH group that is a residue other than H used to form a Ti—O—C bond with a Ti atom, and this is the same Ti atom. A ring structure may be formed by polycondensation with a directly bonded OH group in the molecule, or a repeating structure may be formed by polycondensation between molecules with an OH group directly bonded to another Ti atom. The degree of polymerization in the case of forming a repeating structure is 2-5. When the degree of polymerization is 6 or more, the catalytic activity is lowered and the oligomer component is increased, which causes deterioration of toner blocking properties.

  Preferred as X are residues of dialkanolamine (especially diethanolamine) and residues of trialkanolamine (especially triethanolamine), and particularly preferred are residues of triethanolamine.

  R is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. Specific examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, β-methoxyethyl group, And β-ethoxyethyl group. Among these Rs, H and an alkyl group having 1 to 4 carbon atoms not containing an ether bond are preferable, and H, an ethyl group, and an isopropyl group are more preferable.

In Formula (I), m is an integer of 1-4, Preferably it is an integer of 1-3. n is an integer of 0 to 3, preferably an integer of 1 to 3. The sum of m and n is 4.
In formula (II), p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, a plurality of Xs may be the same or different, but are preferably the same.

  Specific examples of the titanium-containing catalyst (a) in the present invention represented by the general formula (I) include titanium dihydroxybis (triethanolaminate), titanium trihydroxytriethanolaminate, titanium dihydroxybis ( Diethanolaminate), titanium dihydroxybis (monoethanolamate), titanium dihydroxybis (monopropanolamate), titanium dihydroxybis (N-methyldiethanolamate), titanium dihydroxybis (N-butyldiethanolamate), tetrahydroxytitanium and Reaction products with N, N, N ′, N′-tetrahydroxyethylethylenediamine, and intramolecular or intermolecular polycondensates thereof may be mentioned.

  Specific examples of those represented by the general formula (II) include titanyl bis (triethanolaminate), titanyl bis (diethanolaminate), titanyl bis (monoethanolamate), titanyl hydroxyethanolamate, titanylhydroxytriethanolamate, titanyl. Examples include ethoxytriethanolamate, titanyl isopropoxytriethanolamate, and intramolecular or intermolecular polycondensates thereof. Such as a polycondensate.

Among these, preferred are titanium dihydroxybis (triethanolamate), titanium dihydroxybis (diethanolamate), titanylbis (triethanolamate), polycondensates thereof, and combinations thereof, more preferably , Titanium dihydroxybis (triethanolaminate), its polycondensate, in particular titanium dihydroxybis (triethanolamate).
These titanium-containing catalysts (a) can be stably obtained, for example, by reacting commercially available titanium dialkoxybis (alcohol aminate; manufactured by Dupont, etc.) at 70 to 90 ° C. in the presence of water. it can.

  The polycondensation polyester resin constituting the toner binder resin of the present invention can be obtained by further reacting a polyester resin (AX), (AX), which is a polycondensation product of a polyol and a polycarboxylic acid, with a polyepoxide (C) or the like. Examples thereof include modified polyester resin (AY). (AX), (AY) and the like may be used alone or in combination of two or more.

  Examples of the polyol include a diol (g) and a trivalent or higher polyol (h). Examples of the polycarponic acid include a dicarboxylic acid (i) and a trivalent or higher polycarboxylic acid (j). May be.

Examples of the polyester resins (AX) and (AY) include the following, and these can also be used in combination.
(AX1): Linear polyester resin using (g) and (i) (AX2): Non-linear polyester resin using (h) and / or (j) together with (g) and (i) ( AY1): Modified polyester resin obtained by reacting (AX2) with (c)

  As the diol (g), those having a hydroxyl value of 180 to 1900 (mg KOH / g, the same applies hereinafter) are preferable. Specifically, alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexanediol, etc.); carbon number 4 -36 alkylene ether glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polypropylene glycol); alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol and hydrogenation) Bisphenol A and the like; an alkylene oxide having 2 to 4 carbon atoms of the above alicyclic diol [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO) and putylene oxide (hereinafter referred to as BO) Adducts (addition mole number 1-30); adducts (additions) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) having 2 to 4 carbon atoms alkylene oxides (EO, PO, BO, etc.) Mole number 2-30) etc. are mentioned.

Of these, preferred are alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and combinations thereof. Particularly preferred are alkylene oxide adducts of bisphenols, alkylene glycols having 2 to 4 carbon atoms. And a combination of two or more of these.
In the above and below, the hydroxyl value and the acid value are measured by the method defined in JIS K 0070.

  As the trivalent or higher (3 to 8 or higher) polyol (h), those having a hydroxyl value of 150 to 1900 are preferable. Specifically, an aliphatic polyhydric alcohol having 3 to 36 or more carbon atoms having 3 to 8 or more carbon atoms (an alkane polyol and an intramolecular or intermolecular dehydrate thereof such as glycerin, triethylolethane, trimethylolpropane, pentane). Erythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; saccharides and derivatives thereof such as sucrose and methyl glucoside; ) Adduct (addition mole number 1-30); Trisphenols (trisphenol PA etc.) C2-C4 alkylene oxide (EO, PO, BO etc.) adduct (addition mole number 2-30); Novolak Resin (phenol novolac and cresol novola Click like: average polymerization degree of 3 to 60 alkylene oxide (EO 2-4 carbon atoms), PO, BO, etc.) adducts (added mole number 2 to 30) are exemplified.

  Among these, preferred are 3 to 8 or higher aliphatic polyhydric alcohols and alkylene oxide adducts of novolac resins (addition mole number: 2 to 30), and particularly preferred are alkylene oxide adducts of novolak resins. It is.

  As the dicarboxylic acid (i), those having an acid value of 180 to 1250 (mg KOH / g, the same applies hereinafter) are preferable. Specifically, alkane dicarboxylic acids having 4 to 36 carbon atoms (such as succinic acid, adipic acid, and sebacic acid) and alkenyl succinic acids (such as dodecenyl succinic acid); alicyclic dicarboxylic acids having 4 to 36 carbon atoms [dimer acid] (Dimerized linoleic acid) etc.]; C4-C36 alkene dicarboxylic acid (maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.); C8-36 aromatic dicarboxylic acid (phthalic acid, isophthalic acid) , Terephthalic acid, and naphthalenedicarboxylic acid). Of these, preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarponic acids having 8 to 20 carbon atoms. As (i), acid anhydrides or lower alkyl (carbon number 1 to 4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

  The trivalent or higher (3 to 6 or higher) polycarboxylic acid (j) preferably has an acid value of 150 to 1250 mg. Specifically, an aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.); vinyl polymer of unsaturated carboxylic acid [number average molecular weight (hereinafter referred to as Mn, gel permeation chromatography) (By GPC): 450-10000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.), and the like. . Among these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. As the trivalent or higher polycarboxylic acid (j), acid anhydrides or lower alkyl (1 to 4 carbon atoms) esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used.

Further, together with (g), (h), (i) and (j), an aliphatic or aromatic hydroxycarboxylic acid (k) having 4 to 20 carbon atoms and a lactone (l) having 6 to 12 carbon atoms are copolymerized. You can also
Examples of the hydroxycarboxylic acid (k) include hydroxystearic acid and hydrogenated castor oil fatty acid. Examples of the lactone (l) include caprolactone.

  Examples of the polyepoxide (c) include polyglycidyl ether [ethylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, phenol novolac ( Average polymerization degree 3 to 60) glycidyl etherified compound, etc.]; diene oxide (pentadiene dioxide, hexadiene dioxide, etc.) and the like. Among these, polyglycidyl ether is preferable, and ethylene glycol diglycidyl ether and bisphenol A diglycidyl ether are more preferable.

The number of epoxy groups per molecule of (c) is preferably 2-8, more preferably 2-6, and particularly preferably 2-4.
The epoxy equivalent of (c) is preferably 50 to 500. The lower limit is more preferably 70, particularly preferably 80, and the upper limit is further preferably 300, particularly preferably 200. When the number of epoxy groups and the epoxy equivalent are within the above ranges, both developability and fixability are good. It is more preferable if the above-mentioned ranges of the number of epoxy groups per molecule and the epoxy equivalent are satisfied at the same time.

  The reaction ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/2, more preferably 1.5 / 1, as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. ˜1 / 1.3, particularly preferably 1.3 / 1 to 1 / 1.2. The types of polyol and polycarboxylic acid to be used are selected in consideration of molecular weight adjustment so that the glass transition point (Tg) of the polyester toner binder resin finally adjusted is preferably 40 to 90 ° C.

The toner binder resin is required to have different physical properties for full color and monochrome use, and the design of the polyester resin is also different.
That is, since a high-gloss image is required for full color use, it is necessary to use a low-viscosity binder resin. However, for monochrome use, gloss is not particularly required, and hot offset properties are important, so a highly elastic binder resin is used. There is a need.

  (AX1), (AX2), (AY1) and mixtures thereof are preferred for obtaining a high gloss image useful for a full-color copying machine or the like. In this case, since low viscosity is preferable, the ratio of (h) and / or (j) constituting these polyester resins is such that the sum of the number of moles of (h) and (j) is (g) to Preferably it is 0-20 mol% with respect to the sum total of the number of moles of (j), More preferably, it is 0-15 mol%, Especially 0-10 mol%.

  (AX2), (AY1), and mixtures thereof are preferred for obtaining high hot offset resistance useful for monochrome copying machines and the like. In this case, since it is preferable that it is highly elastic, as this polyester resin, what uses both (h) and (j) is especially preferable. The ratio of (h) and (j) is preferably such that the sum of the number of moles of (h) and (j) is 0.1 to 40 mol% with respect to the total number of moles of (g) to (j). More preferably, it is 0.5-25 mol%, especially 1-20 mol%.

In the case of a full-color polyester resin, the temperature (TE) at which the complex viscosity (η *) is 100 Pa · S is preferably 90 to 170 ° C, more preferably 100 to 165 ° C, and particularly 105 to 150 ° C. Sufficient gloss is obtained at 170 ° C. or lower, and heat resistant storage stability is improved at 90 ° C. or higher.
TE is, for example, using a lab blast mill to melt and knead a resin at 130 ° C. and 70 rpm for 30 minutes, and then using a commercially available dynamic viscoelasticity measuring device to change the complex viscosity (η * ) Is measured.

Further, the tetrahydrofuran (THF) insoluble content of the full-color polyester resin is preferably 10% or less, more preferably 5% or less, from the viewpoint of glossiness.
In the above and the following, “%” means “% by weight” unless otherwise specified.
The THF-insoluble content and the THF-soluble content are obtained by the following method.
About 0.5 g of a sample is precisely weighed into a 200 ml stoppered Meyer flask, 50 ml of THF is added, and the mixture is stirred and refluxed for 3 hours. After cooling, the insoluble matter is filtered off with a glass filter. The value (%) of THF-insoluble matter is calculated from the weight ratio of the resin content on the glass filter after vacuum drying at 80 ° C. for 3 hours and the weight of the sample.
Note that this filtrate is used as a THF soluble component for the molecular weight measurement described later.

In the case of a monochrome polyester resin, from the viewpoint of hot offset resistance, the temperature (TG) at which the storage elastic modulus (G ′) of the polyester resin is 6000 Pa is preferably 130 to 230 ° C., more preferably 140 to 230 ° C., In particular, it is 150 to 230 ° C.
For example, TG is a block after melt-kneading a resin at 130 ° C. and 70 rpm for 30 minutes using a laboratory blast mill, and using a commercially available dynamic viscoelasticity measuring device while changing the resin temperature (G ′ ) Is measured.

  From the viewpoint of low-temperature fixability and heat-resistant storage stability, the temperature (TE) at which the complex viscosity (η *) of the monochrome polyester resin becomes 1000 Pa · S is preferably 80 to 140 ° C., more preferably 90 to 135 ° C. In particular, it is 105 to 130 ° C.

  The monochrome polyester resin preferably contains 2 to 70% of THF-insoluble matter, more preferably 5 to 60%, particularly 10 to 50%. When the THF insoluble content is 2% or more, the hot offset resistance is good, and when it is 70% or less, good low-temperature fixability is obtained.

  The peak top molecular weight (Mp) of the polyester resin is preferably 1000 to 30000, more preferably 1500 to 25000, and particularly 1800 to 20000 for both monochrome and full color applications. When Mp is 1000 or more, heat-resistant storage stability and powder fluidity are good, and when it is 30000 or less, the pulverization property of the toner is improved and the productivity is good.

  Further, when the toner binder resin comprising the polyester resin of the present invention is used as a toner, the ratio of the component having a molecular weight of 1500 or less in the toner is preferably 1.8% by weight or less, more preferably 1.3% by weight or less. Particularly preferably, it is 1.1% by weight or less. When the ratio of components having a molecular weight of 1500 or less is 1.8% by weight or less, the storage stability becomes better.

In the above and the following, the ratio of Mp, Mn, and a component having a molecular weight of 1500 or less in the polyester resin or toner is measured under the following conditions using GPC for the THF-soluble component.
Device: Tosoh HCL-8120
Column: TSKgelGMHXL (2)
TSK gelmultiporeHXL-M (1 pc.)
Measurement temperature: 40 ° C
Sample solution: 0.25% THF solution Injection volume: 100 μl
Detector: Refractive index detector Reference substance: Polystyrene The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight (Mp). Furthermore, the abundance ratio of low molecular weight substances is evaluated by the ratio of the peak areas when the molecular weight is 1500.

  The acid value of the polyester resin is preferably 0.1 to 60, more preferably 0.2 to 50, and particularly 0.5 to 40 for both monochrome and full color applications. When the acid value is in the range of 0.1 to 60, the chargeability is good.

  The hydroxyl value of the polyester resin is preferably 1 to 70, more preferably 3 to 60, and particularly preferably 5 to 55 for both monochrome and full color applications. When the acid value is in the range of 1 to 70, the environmental stability is good.

The Tg of the polyester resin is preferably 40 to 90 ° C., more preferably 50 to 80 ° C., particularly 55 to 75 ° C. for both monochrome and full color applications. When the Tg is in the range of 40 ° C. to 90 ° C., the heat resistant storage stability and the low temperature fixability are good.
In the above and the following, the Tg of the polyester resin is measured by a method (DSC method) defined in ASTM D3418-82 using DSC20, SSC / 580 manufactured by Seiko Denshi Kogyo Co., Ltd.

The polyester resin used as the toner binder resin (A) in the present invention can be produced in the same manner as in the usual polyester production method. For example, the reaction temperature is preferably 150 to 280 ° C, more preferably 160 to 250 ° C, particularly preferably 170 to 240 ° C in the presence of a titanium-containing catalyst (a) in an inert gas (nitrogen gas or the like) atmosphere. It can be performed by reacting. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction. It is also effective to reduce the pressure (for example, 1 to 50 mmHg) in order to improve the reaction rate at the end of the reaction.
The addition amount of (a) is preferably 0.0001 to 0.8%, more preferably 0.0002 to 0.6%, particularly preferably 0.0002 to 0.6%, based on the weight of the polymer obtained from the viewpoint of polymerization activity and the like. Preferably it is 0.0015 to 0.55%.

  In addition, other esterification catalysts can be used in combination as long as the catalytic effect of (a) is not impaired. Examples of other esterification catalysts include tin-containing catalysts (eg, dibutyltin oxide), antimony trioxide, titanium-containing catalysts other than (a) (eg, titanium alkoxide, potassium titanyl oxalate, and titanium terephthalate), zirconium-containing catalysts (Eg zirconyl acetate), germanium-containing catalysts, alkali (earth) metal catalysts (eg alkali metal or alkaline earth metal carboxylates: lithium acetate, sodium acetate, potassium acetate, calcium acetate, sodium benzoate, and benzoic acid Potassium), and zinc acetate. The addition amount of these other butterflies is preferably 0 to 0.6% by weight based on the polymer obtained. When the amount is within 0.6% by weight, coloring of the polyester resin is reduced, which is preferable for use in a color toner. The content of (a) in all the added catalysts is preferably 50 to 100% by weight.

  As a production method of the linear polyester resin (AX1), for example, 0.0001 to 0.8% by weight of the butterfly (a) with respect to the weight of the obtained polymer, and if necessary, in the presence of another catalyst. Diol (g), and dicarboxylic acid (i) are heated to 180 ° C. to 260 ° C. and subjected to dehydration condensation under normal pressure and / or reduced pressure conditions to obtain (AX1).

  As a method for producing the non-linear polyester resin (AX2), for example, 0.0001 to 0.8% by weight of the catalyst (a) with respect to the weight of the obtained polymer and, if necessary, the presence of another catalyst. , The diol (g), the dicarboxylic acid (i), and the trivalent or higher polyol (h) are heated to 180 ° C. to 260 ° C. and subjected to dehydration condensation under normal pressure and / or reduced pressure conditions, and then further trivalent or higher. And (AX2) is obtained by reacting the polycarboxylic acid (j). (J) can also be reacted simultaneously with (g), (i) and (h).

Examples of the method for producing the modified polyester resin (AY1) include a method of obtaining (AY1) by adding a polyepoxide (c) to the polyester resin (AX2) and performing a molecular extension reaction of the polyester at 180 ° C. to 260 ° C. .
The acid value of (AX2) to be reacted with (c) is preferably 1 to 60, more preferably 5 to 50. When the acid value is 1 or more, (c) remains unreacted and does not adversely affect the performance of the resin, and when it is 60 or less, the thermal stability of the resin is good.
The amount of (c) used to obtain (AY1) is preferably 0.01 to 10% by weight, more preferably 0, based on (AX2) from the viewpoints of low-temperature fixability and hot offset resistance. 0.05 to 5% by weight.

  In particular, in the present invention, the polycondensation polyester resin is preferably used as a binder resin for a full color toner from the viewpoint of color developability and image strength. In a color image, several types of toner layers are stacked several times, so that the toner layer becomes thick, causing cracks and defects in the image due to insufficient strength of the toner layer, and loss of appropriate gloss. Therefore, the polyester resin is used in order to maintain an appropriate gloss and excellent strength.

In particular, the polyester resin of the binder resin of the present invention has no THF-insoluble content, and the content ratio of the component having a weight molecular weight of 5 × 10 ² or less is 4% by weight or less in the molecular weight distribution in gel permeation chromatography. And preferably has one peak in the region of weight molecular weight 3 × 10 ^{3 to} 9 × 10 ³ . When THF-insoluble matter enters, the glossiness is lowered and the transparency is lowered, and a high-quality image cannot be obtained when an OHP sheet is used. In the toner of the present invention, the molecular weight distribution of the binder resin is such that the weight percent of the weight molecular weight of 5 × 10 ² or less is preferably 4% or less, and the ratio of the weight average molecular weight (Mn) to the number average molecular weight (Mn) is preferably Is defined as 2 ≦ Mw / Mn ≦ 10, so that filming on a blade, a sleeve, or the like hardly occurs. Further, when the component having a weight molecular weight of 5 × 10 ² or less is 4% by weight or more, the blade or sleeve is contaminated by long-term use, and filming is likely to occur.

  Further, the molecular weight distribution of the binder resin used in the toner of the present invention is measured by gel permeation chromatography as follows. The column was stabilized in a heat chamber at 40 ° C., and THF was added to the column at this temperature as a solvent at a flow rate of 1 ml / min. 200 μl is measured. Before injecting the THF sample solution, the THF-insoluble components are removed with a 0.45 μm filter for liquid chromatography.

In measuring the molecular weight of a toner sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Alternatively, the molecular weights manufactured by Toyo Soda Industry Co., Ltd. are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3. It is suitable to use 9 × 10 ⁵ , 8.6 × 105, 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector. The presence or absence of THF-insoluble matter in the binder resin is determined when preparing a THF sample solution for molecular weight distribution measurement. That is, when a 0.45 μm filter unit is attached to the tip of the syringe and the liquid is pushed out of the syringe, it is determined that there is no THF-insoluble matter unless the filter is clogged.

  Moreover, it is preferable that the binder resin used for this invention has the endothermic peak in DSC in the range of 60-70 degreeC. If the temperature is less than 60 ° C., the toner storage stability is affected, causing problems such as solidification of the toner in the cartridge or the hopper. On the other hand, when the temperature exceeds 70 ° C., the toner productivity is affected, and problems such as a decrease in feed during pulverization occur. The endothermic peak in DSC is measured by, for example, Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature rising rate of 10 ° C./min, and the main maximum peak of the endothermic curve is read.

  In addition, as described above, the polyester resin used in the present invention has a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 2 ≦ Mw / Mn ≦ 10. preferable. When Mw / Mn exceeds 10, gloss cannot be obtained when the toner is fixed, and a high-quality image cannot be obtained. Further, if Mw / Mn is less than 2, productivity is reduced in the pulverization step at the time of toner production, and blades and sleeves are contaminated by long-term use, and filming is likely to occur.

  The polyester resin used in the present invention preferably has an acid value of 10 KOHmg / g or less in the interaction between the resin charge control agent and the additive, particularly when a resin charge control agent described later is used. . It is known that the relationship between the chargeability of the polyester resin and the acid value is almost proportional, and that the higher the acid value, the greater the negative chargeability of the resin and, at the same time, affecting the environmental characteristics of charging. That is, when the acid value is high, the charge amount is high under low temperature and low humidity, and the charge amount is low under high temperature and high humidity. Due to changes in the amount of charge due to the environment, changes in background stains, image density, and color reproducibility become large, making it difficult to maintain high image quality. In general, when the acid value exceeds 20 KOHmg / g, there is a risk that an increase in charge amount or deterioration of environmental fluctuations may occur.

  In the polyester resin used in the present invention, the resistance as toner particles is controlled from the chargeability and resistance of the resin charge control agent, hydrophobic silica, and hydrophobic titanium oxide described later. For this reason, when the acid value of the polyester resin exceeds 10 KOH mg / g, the charge control effect of the resin charge control agent, hydrophobic silica, and hydrophobic titanium oxide is inhibited. The acid value of the polyester resin used in the present invention is preferably 10 KOH mg / g or less, more preferably 5 KOH mg / g or less.

Furthermore, the polyester resin used in the present invention preferably has a temperature at which the apparent viscosity by a flow tester is 103 Pa · s is 95 to 120 ° C. If it is less than 95 ° C., there is no margin for hot offset during fixing, while if it exceeds 120 ° C., sufficient gloss cannot be obtained. The temperature at which the apparent viscosity becomes 103 Pa · s is measured using, for example, a CFT-500 model manufactured by Shimadzu Corporation as a flow tester, with a load of 10 kg / cm ² , an orifice diameter of 1 mm × length of 1 mm, and a temperature rising rate of 5 ° C./min. The temperature is measured and the temperature at which the apparent viscosity becomes 103 Pa · s is read.

Next, the resin charge control agent used for the toner of the present invention will be described.
In general, by adding a sulfonate group-containing monomer as a monomer constituting the resin charge control agent, the negative charge imparting effect of the resin charge control agent is improved. On the other hand, since the environmental stability (temperature / humidity stability) of the toner decreases due to hygroscopicity, it is generally known to use an aromatic monomer having an electron-withdrawing group as a copolymer. However, it is sufficient to use several thousand sheets. However, if the toner is used for a long time of tens of thousands or more, contamination of the developing sleeve and the layer thickness regulating member (blade or roller) and photoconductor filming may occur. There is a problem that the charging stability and the high image quality are not sufficiently maintained, and the productivity is lowered.

  In order to compensate for this drawback, the toner of the present invention has (1) a sulfonate group-containing monomer and (2) an electron-withdrawing group as compared with a polyester resin suitable as a binder resin for a full-color toner in terms of color developability and image strength. 4 of (1)-(4) containing the aromatic monomer which has, and (3) 3 types of monomers of an acrylic ester monomer and / or a methacrylic ester monomer, or (4) aromatic vinyl monomer further By using a copolymer containing various monomers as a resin charge control agent, it has excellent charge stability and environmental stability over a long period of time, and there is no contamination of the developing sleeve or the layer thickness regulating member (blade or roller). It is possible to obtain a toner for developing an electrostatic charge image with good layer formation, preventing photoconductor filming, maintaining high image quality, and high productivity.

Further, the weight percent of the weight average molecular weight of 1 × 10 ³ or less is defined for the molecular weight distribution of the resin charge control agent. Components having a weight average molecular weight of 1 × 10 ³ or less are low molecular weight components, copolymers, ionomers, residual monomers, and the like, which inhibit charge generation and are affected by temperature and humidity to change the charge. These ingredients also affect safety such as skin irritation and fish toxicity. When the component having a weight average molecular weight of 1 × 10 ³ or less is 10% by weight or more, it is greatly affected by temperature and humidity and the chargeability becomes unstable.

The effects as described above are presumed to be as follows.
That is, the negative charge imparting effect can be enhanced by using a sulfonate group-containing monomer and an aromatic monomer having an electron withdrawing group in combination. Furthermore, by using acrylic acid ester monomers and / or methacrylic acid ester monomers, in addition to aromatic vinyl monomers, the environmental stability of charging is further enhanced, the resin hardness is increased, the grindability is improved, and the development is improved. There is no contamination of the sleeve or the layer thickness regulating member (blade or roller), and the effect of preventing photoconductor filming is improved.

  In addition, in addition to the low molecular weight components of these resin charge control agents, the resin charge control agent based on the combination of these monomers can be combined with a polyester resin suitable as a binder resin for full-color toners in terms of color development and image strength. A toner for developing an electrostatic image having an appropriate dispersibility and a sharp charge amount distribution can be obtained, and long-term charge stability and high image quality can be obtained.

  Examples of the sulfonate group-containing monomer constituting the resin charge control agent used in the toner of the present invention include aliphatic sulfonate group-containing monomers and aromatic sulfonate group-containing monomers. Examples of aliphatic sulfonate group-containing monomers include alkali metal salts such as vinyl sulfonic acid, allyl vinyl sulfonic acid, 2-acrylamido-2 methylpropane sulfonic acid, methacryloyloxyethyl sulfonic acid, perfluorooctane sulfonic acid, and alkaline earth metals. Salts, amine salts and quaternary ammonium salts. Examples of the aromatic sulfonate group-containing monomer include alkali metal salts such as styrene sulfonic acid, sulfophenyl acrylamide, sulfophenyl maleimide, and sulfophenyl itaconimide, alkaline earth metal salts, amine salts, and quaternary ammonium salts. . Among the metal salts, salts of heavy metals (nickel, copper, zinc, mercury, chromium, etc.) are not preferable from the viewpoint of safety.

  Examples of the aromatic monomer having an electron withdrawing group constituting the resin charge control agent used in the toner of the present invention include styrene substituted products such as chlorostyrene, dichlorostyrene, bromostyrene, fluorostyrene, nitrostyrene, and cyanstyrene, chlorophenyl (meta ) Acrylate, bromophenyl (meth) acrylate, nitrophenyl (meth) acrylate, phenyl (meth) acrylate substitution products such as chlorophenyloxyethyl (meth) acrylate, chlorophenyl (meth) acrylamide, bromophenyl (meth) acrylamide, nitrophenyl ( Phenyl (meth) acrylamide substitution products such as meth) acrylamide, chlorophenylmaleimide, dichlorophenylmaleimide, nitrophenylmaleimide, nitrochlorophenylmale Phenylmaleimide substituents such as de, chlorophenyl itaconic imides, dichlorophenyl itaconic imides, nitrophenyl itaconic imide, phenyl itaconic imide substituents, such as nitro-chlorophenyl itaconate imide, chlorophenyl vinyl ether, and the like phenyl vinyl ether substituents such as nitro phenyl ether. In particular, a phenylmaleimide-substituted product and a phenylitaconimide-substituted product substituted with a chlorine atom or a nitro group are preferable in terms of chargeability and filming resistance.

  Further, the acrylic acid ester monomer and / or methacrylic acid ester monomer constituting the resin charge control agent used in the toner of the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, and propyl (meth) acrylate. N-butyl (meth) acrylate, isobutyl (meth) acrylate, stearyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

  Further, examples of the aromatic vinyl monomer constituting the resin charge control agent used in the toner of the present invention include styrene, vinyl toluene, α-methyl styrene and the like. The composition ratio of each monomer in the resin charge control agent of the present invention is such that the sulfonate group-containing monomer is 1 to 30% by weight, more preferably 2 to 20% by weight, based on the weight of the resin charge control agent. When the sulfonate group-containing monomer is less than 1% by weight, the charge rising performance and the saturation charge amount are not sufficient, and the image tends to be affected. On the other hand, if it exceeds 30% by weight, the environmental stability of charging is deteriorated, the charge amount at high temperature and high humidity is low, and the charge amount at low temperature and low humidity is high, so that the charge stability of toner and the maintenance of high image quality are not sufficient. Further, there is a problem that the developing sleeve and the layer thickness regulating member (blade and roller) are easily contaminated and the photosensitive member filming occurs, and the productivity at the time of toner production by the kneading and pulverizing method is also lowered.

  The aromatic monomer having an electron withdrawing group is 1 to 80% by weight, more preferably 20 to 70% by weight, based on the weight of the resin charge control agent. When the amount of the aromatic monomer having an electron-withdrawing group is less than 1% by weight, the charge amount is not sufficient, and background contamination and toner scattering are likely to occur. On the other hand, when the amount exceeds 80% by weight, the dispersion in the toner is poor, the toner charge amount distribution is widened, and background contamination and toner scattering are likely to occur, and the high image quality cannot be sufficiently maintained.

  The acrylic acid ester monomer and / or methacrylic acid ester monomer is 10 to 80% by weight, more preferably 20 to 70% by weight, based on the resin charge control agent. If the acrylic acid ester monomer and / or methacrylic acid ester monomer is less than 10% by weight, sufficient charging environmental stability cannot be obtained, and the pulverization property at the time of toner production by the kneading and pulverization method is not sufficient, Contamination of the developing sleeve and the layer thickness regulating member (blade and roller) and photoconductor filming cannot be sufficiently prevented. If it exceeds 80% by weight, the rise of charge and the amount of charge are not sufficient, and the image tends to be affected.

  The aromatic vinyl monomer is 0 to 30% by weight, more preferably 3 to 20% by weight, based on the weight of the resin charge control agent. When the amount of the aromatic vinyl monomer exceeds 30% by weight, the resin charge control agent becomes hard, the dispersibility in the toner is lowered, the charge distribution is widened, and background contamination and toner scattering are likely to occur. Further, the toner fixing property, particularly the color developing property when color toners are mixed, becomes poor.

  In the resin charge control agent used in the toner of the present invention, as described above, a phenylmaleimide substituted or phenylitaconimide substituted monomer substituted with a chlorine atom or a nitro group can be used as the aromatic monomer. Variations in volume resistance that may be attributed to residues of catalyst, polymerization inhibitor, solvent, and the like during synthesis of these monomers may occur, affecting the desired toner charge amount. For this reason, there is a possibility that problems such as the rising of the charge of the toner containing the resin negative charge control agent and the charge-up of the saturation charge amount may occur.

  Therefore, in the present invention, a resin charge control agent having a volume resistance in the range of 9.5 to 11.5 Log Ω · cm is used. If the volume resistance of the resin charge control agent is less than 9.5 Log Ω · cm, the toner on the developing roller cannot initially obtain a sufficient charge amount, and scumming or toner scattering occurs. When the volume resistance of the resin charge control agent exceeds 11.5 LogΩ · cm, the toner on the developing roller can initially obtain a desired charge amount, but it is charged up over time. The toner thin layer is not uniform, and color streaks and unevenness occur on the image. In the two-component development method, the image density is lowered, and background staining and toner scattering occur. The volume resistance of the resin charge control agent is more preferably 10.0 to 11.0 LogΩ · cm.

The volume resistance of the resin charge control agent contained in the toner of the present invention is measured according to JIS standard K6911. The resin charge control agent is sized with a mesh and conditioned at 23 ° C. and 50% RH. This sample is molded by an automatic pressure molding machine with a sample amount of 3 g and a pressure of 500 kg / cm ² to produce a disk-shaped test piece having a thickness of about 2 mm and a diameter of 4 cm. The thickness is accurately measured with a caliper, set in a dielectric loss measuring instrument (such as TR-10C manufactured by Ando Electric Co., Ltd.), and an AC voltage having a frequency of 1 kHz is applied to measure the volume resistance.

The resin charge control agent contained in the toner of the present invention preferably has a temperature at which the apparent viscosity by a flow tester is 104 Pa · s is 85 to 110 ° C. When the temperature is less than 85 ° C., an appropriate dispersibility in the toner cannot be obtained, and not only the charging is lowered but also the storage stability is deteriorated and aggregation and solidification are easily caused. Further, in the method obtained from the production process of kneading, pulverization, and classification, sticking in the pulverization process is likely to occur, and productivity is reduced. On the other hand, when the temperature exceeds 110 ° C., the dispersibility in the toner is lowered, the charge amount distribution is widened, and background contamination and toner scattering are easily generated. Further, the toner fixing property, particularly the color developing property when color toners are superimposed, becomes poor. The temperature at which the apparent viscosity becomes 104 Pa · s is measured using, for example, a CFT-500 model manufactured by Shimadzu Corporation as a flow tester, with a load of 10 kg / cm ² , an orifice diameter of 1 mm × length of 1 mm, and a heating rate of 5 ° C./min. The temperature is measured and the temperature at which the apparent viscosity becomes 104 Pa · s is read.

The weight average molecular weight of the resin charge control agent contained in the toner of the present invention is preferably 5 × 10 ³ to 1 × 10 ⁵ . If it is less than 5 × 10 ³ , moderate dispersibility in the toner cannot be obtained and charging is not only reduced, but also in the method of obtaining toner from a production process consisting of kneading, pulverization and classification, fixing in the pulverization process Is prone to occur and decreases productivity. On the other hand, if it exceeds 1 × 10 ⁵ , the dispersibility in the toner is lowered, the charge amount distribution is widened, the background stain or the toner scattering in the machine is likely to occur, and the toner fixability and color developability are poor. Furthermore, it is preferable that the component of the resin charge control agent having a weight average molecular weight of 1 × 10 ³ or less is 10% by weight or less. Components having a weight average molecular weight of 1 × 10 ³ or less are low molecular weight components, copolymers, ionomers, residual monomers, and the like, which inhibit charge generation and are affected by temperature and humidity to change the charge. These ingredients also affect safety such as skin irritation and fish toxicity. The component having a weight average molecular weight of 1 × 10 ³ or less is more preferably 6% by weight or less.

Further, the temperature at which the apparent viscosity of the binder resin of the present invention by a flow tester is 10 ³ Pa · s is T1, and the temperature at which the apparent viscosity of the resin charge control agent by a flow tester is 10 ⁴ Pa · s is T2. In this case, it is preferable that T1 and T2 satisfy the relationship of 0.9 <T1 / T2 <1.4.

  Dispersion of the charge control agent in the binder resin is a major factor that determines the charging performance of the toner. In the present invention, a combination of a specific binder resin and a specific resin charge control agent provides a toner having good chargeability and excellent charge rise. However, as described above, it is clear that the dispersibility (compatibility) between the binder resin and the resin charge control agent affects the charging performance. The inventors paid attention to the apparent viscosities of the binder resin and the resin charge control agent by the individual flow testers and studied the degree of dispersion thereof to obtain the optimum range. When the T1 / T2 ratio is less than 0.9, the apparent viscosity of the binder resin and the resin charge control agent is close to each other, and the binder resin and the resin charge control agent are in a compatible state, resulting in a shortage of the saturated charge amount and a charge rise failure. When the T1 / T2 ratio exceeds 1.4, the apparent viscosity of the binder resin and the resin charge control agent is too far apart, resulting in poor dispersion of the resin charge control agent, initial ground contamination, and a decrease in charge over time. With respect to a specific resin charge control agent, the constitutional monomer, the apparent viscosity, and the apparent viscosity ratio with the binder resin to be dispersed exhibit good chargeability and are less likely to cause filming.

  The addition amount of the resin charge control agent used in the toner of the present invention is preferably 0.1 to 20% by weight, desirably 0.5 to 10% by weight, based on the toner particles. If it is less than 0.1% by weight, the rising of the charge and the charge amount are not sufficient, and the image tends to affect the image such as background stains and dust. If it exceeds 20% by weight, the dispersion becomes poor, the charge amount distribution becomes wide, and background contamination and toner scattering are likely to occur.

As will be described later, the additive used in the toner of the present invention will be described later. When a resin charge control agent is used, the silica having a primary particle size of 0.01 to 0.03 μm and a primary particle size of 0.1. And a specific surface area of 60 to 140 m ² / g of hydrophobized titanium oxide having a specific performance of 01 to 0.03 μm. By using these additives with the polyester resin and the resin charge control agent, a toner having stable chargeability can be obtained.

  That is, by attaching hydrophobically treated silica having a primary particle diameter of 0.01 to 0.03 μm to the surface of the base toner, the required fluidity and chargeability are imparted to the toner, and the toner is exposed on the developing roller and from the developing roller. Developability to the body is improved. The addition amount of this type of silica is preferably 2.1 parts by weight or more with respect to 100 parts by weight of the base toner. This makes the thin layer of the toner uniform on the developing roller and greatly improves the unevenness of the thin layer. Further, the generation of white streaks due to the fusion of the toner to the stirring developer coating blade is prevented by further stirring the developing roller. If the amount is less than this, the toner fluidity may not be sufficiently obtained, and a necessary amount of toner may not be supplied to the developing roller, or a necessary toner charge amount may not be obtained. In addition, the thin layer of the toner on the developing roller becomes non-uniform, and there may be a case where uniform development of the toner and an image cannot be obtained, or white streaks due to fusion of the toner to the stirring developer coating blade may occur.

Further, by adhering hydrophobically treated titanium oxide having a primary particle size of 0.01 to 0.03 μm and a specific surface area of 60 to 140 m ² / g to the surface of the base toner, the charging property of the toner is stabilized. Charge rise and charge up are prevented. The addition amount of this type of titanium oxide is preferably 0.4 to 1.0 part by weight based on 100 parts by weight of the base toner. If the amount is less than 0.4 parts by weight, the toner may be too charged and sufficient toner development may not be performed. On the other hand, when added in an amount of more than 1.0 part by weight, the chargeability of the toner is too low, and the toner may scatter from the developing roller or cause background stains. The base toner means particles in the middle of production containing materials other than additives, at least a binder resin, a colorant, and a resin charge control agent.

In addition to the polycondensed polyester resin, the toner binder resin (A) of the present invention may contain other resins, if necessary.
Other resins include styrene resins (such as copolymers of styrene and alkyl (meth) acrylate, copolymers of styrene and diene monomers), epoxy resins (such as bisphenol A diglycidyl ether ring-opening polymer), Examples thereof include urethane resins (diols and / or polyaddition products of trivalent or higher polyols and diisocyanates, etc.).
The weight average molecular weight of the other resin is preferably 1000 to 2 million.
The content of the other resin in the toner binder resin (A) is preferably 0 to 40% by weight, more preferably 0 to 30% by weight, and particularly preferably 0 to 20% by weight.

When two or more kinds of polyester resins are used in combination, and when at least one kind of polyester resin and another resin are mixed, powder mixing or melt mixing may be performed in advance, or they may be mixed at the time of toner formation.
The temperature at the time of melt mixing is preferably 80 to 180 ° C, more preferably 100 to 170 ° C, and particularly preferably 120 to 160 ° C.
If the mixing temperature is too low, sufficient mixing cannot be achieved, which may result in non-uniformity. When two or more kinds of polyester resins are mixed, if the mixing temperature is too high, averaging due to transesterification occurs, so that the resin physical properties necessary as a toner binder may not be maintained.

The mixing time in the case of melt mixing is preferably 10 seconds to 30 minutes, more preferably 20 seconds to 10 minutes, and particularly preferably 30 seconds to 5 minutes. When two or more kinds of polyester resins are mixed, if the mixing time is too long, averaging due to transesterification occurs, so that the resin physical properties necessary as a toner binder may not be maintained.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous mixing device. In order to uniformly mix at an appropriate temperature in a short time, a continuous mixing device is preferable. Examples of the continuous mixing device include an extruder, a continuous kneader, and a three roll. Of these, extruders and container kneaders are preferred.

In the case of powder mixing, it can be mixed with normal mixing conditions and mixing equipment.
As mixing conditions in the case of powder mixing, the mixing temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. The mixing time is preferably 3 minutes or more, more preferably 5 to 60 minutes. Examples of the mixing device include a Henschel mixer, a Nauter mixer, and a bumper mixer. A Henschel mixer is preferred.

  The electrostatic image developing toner of the present invention comprises at least the toner binder resin (A) of the present invention and a colorant (B), and if necessary, a release agent (C), a charge control agent (D), and Contains various additives such as fluidizing agent (E).

(Coloring agent)
As the colorant (B), known dyes, pigments and magnetic powders can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Parared, Faise Red, Paracro Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyra Ron Red, Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon, magnetite, iron black and mixtures thereof can be used.
The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight based on the toner when a dye or pigment is used.
When magnetic powder is used as a colorant, it is usually 1 to 70% by weight, preferably 15 to 70% by weight, more preferably 30 to 60% by weight, particularly preferably 2 to 30% by weight based on the toner. It is.

  The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded together with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(Release agent)
As the release agent (C), a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface. As a result, it is effective against high temperature offset without applying a release agent such as oil to the fixing roller. Examples of such a wax component include the following. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, And petroleum waxes such as petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .

Preferred examples of the mold release agent (C) include carnauba wax (C1), Fischer-Tropsch wax (C2), paraffin wax (C3), and polyolefin wax (C4).
Examples of (C1) include natural carnauba wax and defree fatty acid type carnauba wax.
(C2) includes petroleum-based Fischer-Tropsch wax (such as Paraflint H1, Paraflint H1N4 and Laughlint C105 manufactured by Schumann-Sazol), natural gas-based Fischer-Tropsch wax (such as FT100 manufactured by Shell MDS), and these Fischer-Tropsch waxes And purified by a method such as fractional crystallization [Nippon Seiwa Co., Ltd. MDP-7000, MDP-7010, etc.].
Examples of (C3) include petroleum wax-based paraffin wax [Nippon Seiwa Co., Ltd. paraffin wax HNP-5, HNP-9, HNP-11, etc.].
Examples of (C4) include polyethylene wax (Sanyo Chemical Industries, Ltd., Sun Wax 171P, Sun Wax LEL400P, etc.), and polypropylene wax (Sanyo Chemical Industries, Ltd., Viscol 550P, Viscol 660P, etc.).
Of these waxes, carnauba wax and Fischer-Tropsch wax are preferred, and carnauba wax and petroleum Fischer-Tropsch wax are more preferred. By using these waxes as release agents, the low-temperature fixability when toner is used is excellent.

  The content of the release agent (C) in the toner is preferably 0 to 15% by weight, more preferably 1 to 10% by weight.

(Charge control agent)
As the charge control agent (D), known ones can be used, for example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, metal-containing azo dyes, rhodamine dyes, alkoxy amines, Quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds, tungsten alone or compounds, fluorine-based activators, quaternary ammonium salt-containing polymers, sulfonic acid group-containing polymers, fluorine-containing Polymer, halogen-substituted aromatic ring-containing polymer, salicylic acid metal salt, salicylic acid derivative metal salt, and the like. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.

  The amount of the charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, but is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is lowered, and the image density is lowered. Invite.

As the charge control agent used in the present invention, the resin charge control agent and those described in claims 11 to 20 are particularly preferable.
The resin charge control agent is as already described.
The toner according to claims 11 to 20 exhibits remarkably good chargeability, and the content in the toner is preferably 0.01 to 20% by weight, more preferably 0.1 to 15% by weight. .

(Fluidizer, toner external additive)
Examples of inorganic fine particles that are external additives as a fluidizing agent (E) added to the toner of the present invention include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, and iron oxide. , Copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate , Silicon carbide, silicon nitride and the like. Among these, a metal oxide, a metal nitride, and a metal carbide are preferable, and an external additive having a number average particle size in the range of 8 to 80 nm and an external additive in the range of 120 to 300 nm are preferable. Among the inorganic fine particles, silica, alumina, and titanium oxide are preferable, and silica and titanium oxide are particularly preferable. Further, it is more preferable in terms of toner chargeability and fluidity that at least the primary particles contain titanium oxide having a primary particle number average particle size of 5 to 40 nm.
The external additive such as inorganic fine particles is more preferably used in an amount of 0.01 to 5% by weight based on the toner base.
As a means of highly controlling the fluidity of the toner, not only the control of the production conditions of the external additive, but also the crushing, sieving and the like after the production of the external additive are effective. The adhesion state is also important.

As the external additive, inorganic fine particles or hydrophobized inorganic particles can be used in combination. The average particle size of the hydrophobized primary particles is 1 to 20 nm, more preferably 6 to 15 nm (specific surface area according to the BET method). 100 to 400 m ² / g), and 30 to 150 nm, more preferably 90 to 130 nm ( ²⁰ to 100 m ² / g specific surface area according to the BET method) and at least two kinds of large particle size inorganic fine particles More preferably, the above is present on the toner surface. More preferably, the small particle size inorganic fine particles are silica or titanium oxide, and both are more preferable. Silica is more preferable for the large particle size inorganic fine particles. Further, silica produced by a wet method such as a sol-gel method is more preferable. Further, it is more preferable that inorganic fine particles having a medium particle diameter of 20 to 50 nm (specific surface area by BET method of 40 to 100 m ² / g), more preferably silica, are further present on the toner surface.

  Any known inorganic fine particles can be used as long as the conditions are satisfied. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), fluoropolymers, and the like may be contained.

  Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H 1303 (above Hoechst) and R972, R974, RX200, RY200, R202, R805, and R812 (above Nippon Aerosil). Further, as titania fine particles, P-25 (Nippon Aerosil), STT-30, STT-65C-S (above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600B MT-150A (taker above). Particularly, the hydrophobized titanium oxide fine particles include T-805 (Nippon Aerosil), STT-30A, STT-65S-S (above Titanium Industry), TAF-500T, TAF-1500T (above Fuji Titanium Industry), MT -100S, MT-100T (above Taka), IT-S (Ishihara Sangyo), etc.

  In order to obtain hydrophobized oxide fine particles, silica fine particles, titania fine particles, and alumina fine particles, hydrophilic fine particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl modified silicone oil, fluorine modified silicone oil, polyether modified silicone oil, alcohol modified silicone oil, amino modified silicone. Oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like can be used. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, quartz sand, clay, mica, and silica ash. Examples thereof include stone, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Of these, silica and titanium dioxide are particularly preferred. The addition amount can be 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the toner. The average particle size of the primary particles of the inorganic fine particles is 100 nm or less, preferably 3 nm or more and 70 nm or less. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. On the other hand, if it is larger than this range, the surface of the photoreceptor is undesirably damaged.

  Other external additives and fluidizing agents include polymer-based fine particles such as soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polystyrene, methacrylic acid ester and acrylic acid ester copolymer, silicone, benzoguanamine, Examples of the polymer particles include a polycondensation system such as nylon and a thermosetting resin.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  The toner of the present invention includes other additives such as fluoropolymers, low molecular weight polyolefins, metal oxides (such as aluminum oxide, tin oxide, and antimony oxide), conductivity imparting agents (such as carbon black and tin oxide), magnetic materials, Furthermore, you may use together what surface-treated those additives. These additives may be used alone or in combination of two or more, and the content is generally 0.1 to 10 parts by weight with respect to 100 parts by weight of the toner.

The charge control agent and the release agent can be melt-kneaded together with the master batch and the binder resin, or may be added when dissolved and dispersed in an organic solvent.
As a method of adding to the toner, not only dry external addition treatment using a Henschel mixer, Q mixer, etc., but also wet external addition treatment (solvent, water (containing an activator for improving wettability as required)). Adhesion is also effective.
The external additive is mixed into the base toner. The external additive is added to the base toner by mixing and stirring the base toner and the external additive using a mixer while the external additive is crushed on the toner surface. It may be a dry mix to be coated. At this time, it is important in terms of durability that external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the base toner. As these addition conditions, the blade shape of the mixer, the number of rotations, the mixing time, the number of times of mixing, the amount of the external additive, the amount of the base toner, and the surface properties (unevenness, hardness, viscoelasticity, etc.) of the base toner are important.

Moreover, an inorganic fine particle adhesion process can be performed in a liquid as wet mixing. This step may be performed after the toner particles are formed in water and the used surfactant and the like are removed by washing. Excess surfactant present in water is removed by solid-liquid separation such as filtration and centrifugation, and the resulting cake and slurry are redispersed in an aqueous medium. Further, inorganic fine particles are added and dispersed in the slurry. Inorganic fine particles can be dispersed in an aqueous dispersion in advance. At that time, if dispersed using a surfactant having a reverse polarity, adhesion to the surface of the toner particles is more efficiently performed. In addition, when the inorganic fine particles are hydrophobized and are difficult to disperse in the aqueous dispersion, the inorganic fine particles may be dispersed after the interfacial tension is lowered by using a small amount of alcohol or the like to facilitate wetting. Thereafter, an aqueous surfactant solution having a reverse polarity is gradually added with stirring. The reverse polarity surfactant is preferably used in an amount of 0.01 to 1% by weight based on the solid content of the toner particles. By adding a surfactant having a reverse polarity, the charge of the inorganic fine particle dispersion in water is neutralized, and the inorganic fine particles can be aggregated and adhered to the surface of the toner particles. The inorganic fine particles are preferably used in an amount of 0.01 to 5% by weight based on the solid content of the toner particles.
The inorganic fine particles adhered to the toner surface can be fixed to the toner surface by heating the slurry thereafter to prevent detachment. At that time, it is desirable to heat at a temperature higher than the Tg of the resin constituting the toner. Further, heat treatment may be performed after drying while preventing aggregation.

  Further, in order to lower the coefficient of friction on the surface of the photoreceptor and improve the cleaning property, a metal stearate may be mixed as a lubricant in the toner of the present invention. Zinc stearate is preferred.

(Production method)
The electrostatic image developing toner of the present invention can be produced by a conventionally known pulverization method or polymerization method. For example, an airflow pulverization method, a mechanical pulverization method, an emulsion aggregation method, a suspension method Examples thereof include a polymerization method, and the production method does not impair the effects of the invention.
As a toner production method, for example, in the case of a known kneading and pulverizing method, the toner constituents are dry-blended, melt-kneaded, then finely pulverized using a jet mill or the like, and further subjected to air classification, It is obtained as particles having a volume average particle diameter of 2 to 10 μm.
The volume average particle diameter is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter, Inc.)].

  The method for producing the toner of the present invention may be any conventionally known method. Specifically, for example, a step of mechanically mixing at least a binder resin, a charge control agent and a toner component of a colorant, and a step of melt-kneading And a toner manufacturing method having a pulverizing step and a classification step. In addition, in the mechanical mixing step and the melt-kneading step, a production method is also included in which powder other than the particles obtained as a product obtained in the pulverization or classification step is returned and reused.

  The powders (sub-products) other than the particles used as the product referred to here are fine particles and coarse particles other than the components used as the product having a desired particle size obtained in the pulverization step after the melt-kneading step, and subsequent classification. It means fine particles or coarse particles other than the components that are produced in the process and have a desired particle size. It is preferable to mix 1 to 20 parts by weight of the by-product with the raw material and preferably the main raw material 100 in the step of mixing or melt-kneading such a by-product.

  Mixing step of mechanically mixing at least binder resin, colorant, resin charge control agent and other charge control agent toner components, and mechanically adding toner components including binder resin, colorant, charge control agent and by-products The mixing step for mixing may be performed under normal conditions using a normal mixer with rotating wings, and is not particularly limited.

  When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Kay Sea Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works Co., Ltd. A kneader or the like is preferably used. It is important that this melt-kneading is performed under appropriate conditions that do not cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature should be performed with reference to the softening point of the binder resin. If the temperature is too low from the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed.

  When the above melt-kneading process is completed, the kneaded product is then pulverized. In this pulverization step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used. After the pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like to produce a developer having a predetermined particle size, for example, an average particle size of 5 to 20 μm.

  In order to produce the toner of the present invention, the hydrophobic silica fine powder listed above for the base toner produced as described above in order to improve fluidity, storage stability, developability and transferability as a developer. Add and mix inorganic fine particles. For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.

The toner of the present invention using the toner binder resin of the present invention is surfaced with magnetic powder (iron powder, nickel powder, ferrite, magnetite, etc.), glass beads and / or resin (acrylic resin, silicone resin, etc.) as necessary. Is mixed with carrier particles such as ferrite coated with, and used as a two-component developer of an electric latent image. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electric latent image.
Subsequently, it is fixed on a support (paper, polyester film, etc.) by a known hot roll fixing method to obtain a recording material.

In recent years, in order to obtain high-definition and high-quality images, there is a tendency to further reduce the particle diameter of toner. Although the particle size may be reduced by a manufacturing method based on ordinary kneading and pulverization methods, the cost is extremely high from the viewpoint of energy used and yield, and there is a pulverization limit of the particle size. I can not cope.
Therefore, as a method for solving this problem, a polymerized toner production method such as a suspension polymerization method, an emulsion polymerization aggregation method, or a dispersion polymerization method has been proposed.

The toner according to the present invention has a volume average particle diameter of 2 to 10 μm, and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.00 to 1.40. It is preferable that it exists in.
By using a toner having a small particle diameter, the toner can be densely attached to the electrostatic charge image. However, when the volume average particle diameter is smaller than the range of the present invention, in the two-component developer, the toner is fused to the surface of the magnetic carrier during a long period of stirring in the developing device, and the charging ability of the magnetic carrier is lowered. On the contrary, when the volume average particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed. In many cases, the variation in toner particle size becomes large.

Further, by narrowing the particle size distribution, the toner charge amount distribution becomes uniform, a high-quality image with little background fogging can be obtained, and the transfer rate can be increased. However, it is not preferable that Dv / Dn exceeds 1.40 because the charge amount distribution becomes wide and the resolving power decreases.
The average particle diameter and particle size distribution of the toner can be measured using a Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, a Coulter counter TA-II type was used and connected to an interface (manufactured by Nikka Giken) and a personal computer (PC9801: manufactured by NEC) for outputting the number distribution and volume distribution.

The toner according to the present invention preferably has a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180.
2 and 3 are diagrams schematically showing the shape of the toner in order to explain the shape factor SF-1 and the shape factor SF-2. The shape factor SF-1 indicates the ratio of the roundness of the toner shape and is represented by the following formula (1). This is a value obtained by dividing the square of the maximum length MXLNG of the shape formed by projecting the toner on a two-dimensional plane by the figure area AREA and multiplying by 100π / 4.

ＳＦ−１の値が１００の場合トナーの形状は真球となり、ＳＦ−１の値が大きくなるほど不定形になる。

When the value of SF-1 is 100, the shape of the toner becomes a true sphere, and becomes larger as the value of SF-1 increases.

  The shape factor SF-2 indicates the ratio of the unevenness of the toner shape, and is represented by the following formula (2). A value obtained by dividing the square of the perimeter PERI of the figure formed by projecting the toner on the two-dimensional plane by the figure area AREA and multiplying by 100π / 4.

ＳＦ−２の値が１００の場合トナー表面に凹凸が存在しなくなり、ＳＦ−２の値が大きくなるほどトナー表面の凹凸が顕著になる。

When the value of SF-2 is 100, there is no unevenness on the toner surface, and as the value of SF-2 increases, the unevenness of the toner surface becomes more prominent.

When the shape of the toner is close to a spherical shape, the contact between the toner and the toner or the toner and the photoreceptor 1 is close to a point contact, so that the adsorbing force between the toners is weakened and the fluidity is increased. The attracting force with the body 1 is also weakened, and the transfer rate is increased. On the other hand, since spherical toner tends to enter the gap between the cleaning blade 7a and the photoreceptor 1, the toner shape factor SF-1 or SF-2 is preferably large to some extent. Further, when SF-1 and SF-2 are increased, toner is scattered on the image and the image quality is lowered. For this reason, it is preferable that SF-1 and SF-2 do not exceed 180.
Specifically, the shape factor is measured by taking a photograph of the toner with a scanning electron microscope (FE-SEM S-4800: manufactured by Hitachi, Ltd.), and using this image analysis apparatus (Luzex AP: manufactured by Nireco). Introduced, analyzed and calculated.

The toner suitably used in the image forming apparatus of the present invention is, for example, a toner material in which at least a polyester prepolymer having a functional group containing a nitrogen atom, a polyester resin, a colorant, and a release agent are dispersed in an organic solvent. It is a toner obtained by crosslinking and / or extending the liquid in an aqueous solvent. Note that at least the polycondensation polyester resin of the present invention is used as a raw material polyester resin.
In the following, description will be made with reference to examples of such toner constituent materials and manufacturing methods.

(Modified polyester)
The toner according to the present invention contains a modified polyester (i) as a binder resin. The modified polyester (i) refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin through a covalent bond or an ionic bond. Specifically, the polyester terminal is modified by introducing a functional group such as a carboxylic acid group or an isocyanate group that reacts with a hydroxyl group into the polyester terminal and further reacting with an active hydrogen-containing compound.

  Examples of the modified polyester (i) include urea-modified polyester obtained by a reaction between a polyester prepolymer (A) having an isocyanate group and amines (B). As the polyester prepolymer (A) having an isocyanate group, a polyester having a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and having an active hydrogen group is further added to a polyvalent isocyanate compound (PIC). And those reacted with. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

The urea-modified polyester is produced as follows.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable. Examples of the dihydric alcohol (DIO) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyhydric alcohol (TO) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred. Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) ); Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.

  The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acid (B5), and amino acid block of B1 to B5 (B6).
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  The modified polyester (i) used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10000, and if it is less than 1000, the elongation reaction hardly occurs and the elasticity of the toner is small, and as a result, the hot offset resistance deteriorates. On the other hand, when it exceeds 10,000, the problem in production becomes high in the deterioration of fixability, particle formation and pulverization. The number average molecular weight of the modified polyester (i) is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.

In the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B) to obtain the modified polyester (i), a reaction terminator is used as necessary to adjust the molecular weight of the resulting urea-modified polyester. be able to. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
The molecular weight of the polymer produced can be measured using gel permeation chromatography (GPC) with THF as a solvent.

(Unmodified polyester)
In the present invention, not only the modified polyester (i) is used alone, but also the unmodified polyester (ii) can be contained as a binder resin component together with the (i). By using (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to the single use. Examples of (ii) include polycondensates of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC), which are the same as the polyester component (i), and preferred ones are also the same as (i). . Further, (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, for example, may be modified with a urethane bond. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, the polyester component (i) and (ii) preferably have similar compositions. In the case of containing (ii), the weight ratio of (i) to (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. If the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is 1000-10000 normally, Preferably it is 2000-8000, More preferably, it is 2000-5000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. As for the acid value of (ii), 1-5 are preferable, More preferably, it is 2-4. Since a high acid value wax is used for the wax, the binder is easy to match with the toner used for the two-component developer because the low acid value binder leads to charging and high volume resistance.

The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C, preferably 55 to 65 ° C. If it is less than 35 ° C., the heat resistant storage stability of the toner is deteriorated, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners. Show.
The glass transition point (Tg) can be measured with a differential scanning calorimeter (DSC).

(Career)
In addition, when the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. 10 parts by weight is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier, and glass beads having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include phenol resins and amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins. Resin, halogenated olefin resin such as polyvinyl chloride and polyvinylidene chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyfluorocarbon, polyvinyl fluoride resin, polyfluoride Vinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and Copolymers of vinyl, fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluoride monomers including, and silicone resins. In particular, the silicone resin-coated carrier is excellent from the viewpoint of the developer life. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The mixing ratio of the toner and carrier of the two-component developer is usually 0.5 to 20.0 parts by weight of toner with respect to 100 parts by weight of carrier.

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Magnetic material)
Furthermore, the toner of the present invention contains a magnetic material and can be used as a magnetic toner. When a magnetic toner is used, the toner particles may contain magnetic fine particles. As such a magnetic material, iron oxide (ferrite, magnetite, hematite) and other irons, nickel, cobalt and other metals or alloys exhibiting ferromagnetism, compounds containing these elements, or containing no ferromagnetic elements are suitable. Alloys that exhibit ferromagnetism when subjected to various heat treatments, for example, alloys such as manganese copper aluminum, manganese-copper-tin, etc., called Heusler alloys containing manganese and copper, chromium dioxide, etc. Can do. It is preferable that the magnetic substance is contained in a uniformly dispersed form in the form of a fine powder having an average particle size of usually 0.1 to 2 μm, preferably 0.1 to 1 μm. The content of the magnetic material is usually 5 to 150 parts by weight, more preferably 10 to 70 parts by weight, and particularly preferably 20 to 50 parts by weight with respect to 100 parts by weight of the toner obtained.

(Measurement method of softening point)
Using a flow tester, the temperature is raised at a constant speed under the following conditions, and the temperature at which the outflow amount becomes 1/2 is defined as the softening point.
Apparatus: Shimadzu Corporation flow tester CTF-500D
Load: 20 kgf / cm ²
Die: 1mmφ-1mm
Temperature increase rate: 6 ° C / min
Sample amount: 1.0 g

(Particle size measurement method)
As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using first grade sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

(Roundness)
The average circularity E can be measured by a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation). As a specific measuring method, 0.3 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 120 ml of water from which impure solids have been removed in advance, and about 0.2 g of a measurement sample is further added. Add. The suspension in which the sample is dispersed is obtained by carrying out a dispersion treatment with an ultrasonic disperser for about 2 minutes and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of about 5000 / μl.

(SF-1, SF-2)
300 toner SEM images obtained by FE-SEM (S-4800) manufactured by Hitachi, Ltd. were randomly sampled, and the image information was sent to the Nireco image analyzer (Luzex AP) via the interface. It was introduced and analyzed.

(Degree of aggregation)
The method for measuring the accelerated aggregation degree is as follows. The measuring device is a powder tester manufactured by Hosokawa Micron Co., Ltd., and the attached parts are set on the shaking table in the following procedure.
(B) Vibro chute (b) Packing (c) Space ring (d) Flue (3 types) Top>Medium> Bottom (e) Oseva The measurement conditions are as follows.
Flute opening (top) 75μm
中 (Medium) 45μm
〃 (Bottom) 22μm
Swing scale 1mm
Sampling amount 2g
Vibration time 15 seconds After measurement, the degree of aggregation is obtained from the following calculation.
% By weight of powder remaining on the upper sieve × 1 (a)
Weight% of powder remaining on middle stage sieve x 0.6 (b)
% By weight of powder remaining on the lower screen × 0.2 (c)
The total of the above three calculated values is defined as the degree of aggregation (%). That is,
Aggregation value (%) = (a) + (b) + (c).

(Glass transition temperature (Tg))
The Tg of the toner of the present invention was measured under the following conditions using the following differential scanning calorimeter.
・ Differential scanning calorimeter: SEIKO1DSC100
SEIKO1SSC5040 (Disk Station)
·Measurement condition:
Temperature range: 25-150 ° C
Temperature increase rate: 10 ° C / min
Sampling time: 0.5 sec
Sample amount: 10mg

(Volume resistivity)
The volume resistivity of the present invention refers to a high resist meter (for example, manufactured by Advantest Co., Ltd.), in which a pressed toner is placed on a pellet between parallel electrodes separated by a gap of 2 mm, DC 1000V is applied between both electrodes, The value (logarithmic value) obtained by converting the value measured in TR8601) from the resistance value and pellet thickness and converting it to volume resistivity.

(Developer)
In the image forming apparatus according to the present exemplary embodiment, a charging device, an exposure device, a developing device, a transfer device, a cleaning device, and the like are sequentially arranged around a photoconductor as an image carrier. In addition, a paper feeding / conveying device that feeds the transfer paper from the paper feeding tray and a fixing device that fixes the toner onto the transfer paper after the transfer paper on which the toner image has been transferred are separated from the photoreceptor. In the image forming apparatus configured as described above, the surface of the rotating photoconductor is uniformly charged by the charging device and then irradiated with the laser beam of the exposure device based on the image information to form a latent image on the photoconductor. Form. A toner image is formed by attaching toner charged by a developing device to the electrostatic latent image formed on the photoreceptor. On the other hand, the transfer paper is fed from a paper feed tray by a paper feed / conveyance device, and then conveyed to a transfer portion where the photoconductor and the transfer device face each other. The transfer device applies a charge having a polarity opposite to that of the toner image on the photoconductor to the transfer paper, thereby transferring the toner image formed on the photoconductor to the transfer paper. Next, the transfer paper is separated from the photoconductor, sent to a fixing device, and an image is obtained by fixing the toner to the transfer paper.

  FIG. 1 is a schematic configuration diagram of a developing device (1) of an image forming apparatus according to the present embodiment. The developing device (1) employed in the image forming apparatus will be described in detail with reference to FIG. The developing device (1) is disposed on the side of the photoreceptor (8), and serves as a developer carrying member that carries a two-component developer (hereinafter referred to as “developer”) containing toner and a magnetic carrier on the surface. The non-magnetic developing sleeve 7 is provided. The developing sleeve 7 is attached so as to be partially exposed from an opening formed on the photosensitive member (1) side of the developing casing, and is rotated in the direction of arrow b in the drawing by a driving device (not shown). The material of the developing sleeve is not particularly limited as long as it is used in a normal developing device, and nonmagnetic materials such as stainless steel, aluminum, ceramics, and those coated thereon are used. Further, the shape of the developing sleeve is not particularly limited. Further, a magnet roller (not shown) composed of a fixed magnet group as a magnetic field generating means is fixedly arranged inside the developing sleeve (7). Further, the developing device (1) includes a doctor (9) as a developer regulating member made of a rigid body that regulates the amount of developer carried on the developing sleeve (7). A developer accommodating portion (4) for accommodating a developer is formed on the upstream side of the rotation direction of the developing sleeve (7) with respect to the doctor (9), and the developer in the developer accommodating portion (4) is agitated. First and second stirring screws (5, 6) to be mixed are provided. Also, a toner replenishing port (23) disposed above the developer accommodating portion (4), a toner hopper (2) filled with toner replenished to the developer accommodating portion (4), and a toner replenishing port (23) A toner flow device (3) for connecting the toner hopper (2) is provided.

In the developing device (1) configured as described above, the developer in the developer container (4) is stirred by rotating the first and second stirring screws (5, 6), and the toner, the magnetic carrier, Are triboelectrically charged with opposite polarities. This developer is supplied to the peripheral surface of the developing sleeve (7) that is rotationally driven in the direction of arrow b, and the supplied developer is carried on the peripheral surface of the developing sleeve (7), and the developer sleeve (7) is rotated. , And conveyed in the rotation direction (arrow b direction). Next, the amount of the conveyed developer is regulated by the doctor (9), and the regulated developer is conveyed to a development area where the photoconductor (8) and the development sleeve 7 face each other. In this developing region, the toner in the developer is electrostatically transferred to the electrostatic latent image on the surface of the photoreceptor (8), and the electrostatic latent image is visualized as a toner image.
Here, the distance (development gap; Gp) between the image carrier (8) and the developing sleeve (7) is more preferably 0.01 mm to 0.7 mm, and in the case of less than 0.01, the developer This is not preferable because the transportability of the sheet is reduced and the uniformity of the solid image is decreased. On the other hand, when it exceeds 0.7 mm, the charge rising property and retention of the developer are likely to be lowered, which is not preferable.

-Intermediate transfer member-
FIG. 4 will be described with respect to one embodiment of the intermediate transfer member of the transfer system in the present invention. Around a photosensitive drum (hereinafter referred to as a photosensitive member) 10 as an electrostatic charge image carrier, a charging roller (20) as a charging device, an exposure device (30), a cleaning device (60) having a cleaning blade, a static elimination A neutralizing lamp (70) as a device, a developing device (40), and an intermediate transfer member (50) as an intermediate transfer member are provided. The intermediate transfer member (50) is suspended by a plurality of suspension rollers (51), and is configured to run endlessly in the direction of the arrow by a driving unit such as a motor (not shown). A part of the suspension roller (51) also serves as a transfer bias roller for supplying a transfer bias to the intermediate transfer member, and a predetermined transfer bias voltage is applied from a power source (not shown). A cleaning device (90) having a cleaning blade for the intermediate transfer member (50) is also provided. Further, a transfer roller (80) is disposed as a transfer means for transferring the developed image onto the transfer paper (100) as the final transfer material, facing the intermediate transfer body (50), and the transfer roller (80). Is supplied with a transfer bias by a power supply device (not shown). Around the intermediate transfer member (50), a corona charger (52) is provided as a charge applying unit.

  The developing device (40) includes a developing belt (41) as a developer carrying member, a black (hereinafter referred to as Bk) developing unit (45K) and yellow (hereinafter referred to as Yk) arranged around the developing belt (41). Development unit (45Y), magenta (hereinafter referred to as magenta) development unit (45M), and cyan (hereinafter referred to as C) development unit (45C). Further, the developing belt (41) is stretched between a plurality of belt rollers, and is configured to run endlessly in a direction of an arrow by a driving unit such as a motor (not shown), and a contact portion with the photoreceptor (10). Then, it moves at almost the same speed as the photoconductor (10).

Since the configuration of each developing unit is common, the following description will be given only for the Bk developing unit (45K), and the other developing units (45Y, 45M, 45C) are those in the Bk developing unit (45K) in the figure. In the corresponding parts, Y, M and C are added after the numbers given to those in the unit, and the description is omitted. The developing unit (45K) includes a developing tank (42K) that contains a high-viscosity, high-concentration liquid developer containing toner particles and a carrier liquid component, and a lower portion that serves as the liquid developer in the developing tank (42K). A drawing roller (43K) disposed so as to be immersed, and a coating roller (44K) for thinning the developer drawn from the drawing roller (43K) and applying it to the developing belt (41) Yes. The application roller (44K) has conductivity, and a predetermined bias is applied from a power source (not shown).
In addition to the apparatus configuration shown in FIG. 4, the apparatus configuration of the image forming apparatus according to the present embodiment includes each color developing unit around one photoconductor (10) as shown in FIG. A device configuration may be provided.

  Next, the operation of the image forming apparatus according to the present embodiment will be described. In FIG. 4, the photosensitive member (10) is uniformly charged by the charging roller (20) while being driven to rotate in the direction of the arrow, and then the reflected light from the document is imaged and projected by an optical system (not shown) by the exposure device (30). Thus, an electrostatic charge image is formed on the photoconductor (10). This electrostatic charge image is developed by the developing device (40) to form a toner image as a visible image. The developer thin layer on the developing belt (41) is peeled off from the belt (41) in a thin layer state by contact with the photoreceptor in the developing region, and a latent image is formed on the photoreceptor (10). Transition to the part. The toner image developed by the developing device (40) is transferred to the intermediate transfer member (50) at a contact portion (primary transfer region) between the photosensitive member (10) and the intermediate transfer member (50) moving at a constant speed. (Primary transfer). When transferring three or four colors to be superimposed, this process is repeated for each color to form a color image on the intermediate transfer member (50).

  The corona charger (52) for applying an electric charge to the superimposed toner image on the intermediate transfer member, the photosensitive member (10) and the intermediate transfer member (in the rotation direction of the intermediate transfer member (50)). 50) on the downstream side of the contact facing portion and the upstream side of the contact facing portion between the intermediate transfer member (50) and the transfer paper (100). Then, the corona charger (52) gives the toner image a true charge having the same polarity as the charging polarity of the toner particles forming the toner image, so that the toner image can be satisfactorily transferred to the transfer paper (100). A sufficient charge is applied to the toner image. The toner image is charged by the corona charger (52) and then transferred onto the transfer paper (100) conveyed in the direction of the arrow from a paper supply unit (not shown) by a transfer bias from the transfer roller (80). Batch transfer (secondary transfer). Thereafter, the transfer paper (100) onto which the toner image has been transferred is separated from the photoreceptor (10) by a separation device (not shown), and after being subjected to a fixing process by a fixing device (not shown), the transfer paper (100) is discharged from the device. On the other hand, after the transfer, the untransferred toner is collected and removed by the cleaning device (60), and the residual charge is discharged by the discharging lamp (70) in preparation for the next charging.

As described above, the static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably from several Ωcm to 10 ³ Ωcm. By setting the volume resistance to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means is less likely to remain on the intermediate transfer member. Transfer unevenness can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

The material of the intermediate transfer member is not particularly limited, and known materials can be used. An example is shown below. (1) A material having a high Young's modulus (tensile modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT ( Polyalkylene terephthalate) blend materials, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend materials, carbon black dispersed thermosetting polyimide, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation. (2) A belt having a two- or three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery thereof. Therefore, the line image has a performance capable of preventing the line image from being lost. (3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the width of the belt is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .
Conventionally, fluororesin, polycarbonate resin, polyimide resin, and the like have been used for the intermediate transfer belt. However, in recent years, an elastic belt in which the entire belt layer or a part of the belt is used as an elastic member has been used. The transfer of a color image using a resin belt has the following problems.

A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has a high hardness and does not deform according to the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur.
Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. When the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated.

  Therefore, the elastic belt is used for the following purposes when transferring to the sheet. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local irregularities, the paper does not have excessive flatness and has good adhesion without excessively increasing the transfer pressure on the toner layer. In contrast, a transfer image with excellent uniformity can be obtained.

  The elastic belt resin is polycarbonate, fluororesin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer. Styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (for example, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene- Octyl acrylate copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (for example, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacrylic acid). Acid phenyl copolymer, etc.), styrene -Styrenic resins (monopolymer or copolymer containing styrene or a styrene-substituted product) such as methyl α-chloroacrylate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, methyl methacrylate resin, methacrylic acid Butyl resin, ethyl acrylate resin, butyl acrylate resin, modified acrylic resin (for example, silicone-modified acrylic resin, vinyl chloride resin-modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, Vinyl chloride-vinyl acetate copolymer, rosin-modified maleic resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane resin, silica One or a combination of two or more selected from the group consisting of carbon resins, ketone resins, ethylene-ethyl acrylate copolymers, xylene resins and polyvinyl butyral resins, polyamide resins and modified polyphenylene oxide resins can be used. . However, it is a matter of course that the material is not limited to the above materials.

  Elastic rubbers and elastomers include butyl rubber, fluorine rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene rubber natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene ter Polymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, ricone rubber, fluororubber, polysulfide rubber, polynorbornene rubber, hydrogenated nitrile rubber , Selected from the group consisting of thermoplastic elastomers (for example, polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea, polyester, fluororesin) It is possible to use one kind or two or more kinds of combinations that. However, it is a matter of course that the material is not limited to the above materials.

  There are no particular restrictions on the conductive agent for adjusting the resistance value. For example, carbon black, graphite, metal powder such as aluminum and nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite Conductive metal oxides such as oxides (ATO) and indium oxide-tin oxide composite oxides (ITO), and conductive metal oxides are coated with insulating fine particles such as barium sulfate, magnesium silicate and calcium carbonate But you can. Of course, the conductive agent is not limited thereto.

  The surface layer material and the surface layer are required to prevent contamination of the photoconductor by the elastic material, reduce the surface friction resistance to the transfer belt surface, reduce the adhesion of the toner, and improve the cleaning property and the secondary transfer property. . For example, materials that use one or a combination of two or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and increase lubricity, such as fluorine resin, fluorine compound, fluorocarbon, titanium dioxide, silicon carbide, etc. These powders and particles can be used by dispersing one type, two or more types, or a combination of particles having different particle sizes. Further, it is also possible to use a material having a reduced surface energy by forming a fluorine-rich layer on the surface by heat treatment, such as a fluorine-based rubber material.

~ Charging device ~
FIG. 6 is a schematic diagram showing a part of a configuration of an image forming apparatus using a contact-type charging device. The photosensitive member (140) as the member to be charged and the electrostatic charge image carrier is rotationally driven in the direction of the arrow at a predetermined speed (process speed). The charging roller (160), which is a charging member brought into contact with the photosensitive drum, is basically composed of a cored bar and a conductive rubber layer formed concentrically on the outer periphery of the cored bar, and both ends of the cored bar are not shown. In addition to being held freely rotating by a bearing member or the like, the photosensitive drum is pressed with a predetermined pressing force by a pressing means (not shown). In this case, the charging roller (160) rotates the photosensitive member 140. Rotates following the drive. The charging roller (160) is formed to have a diameter of 16 mm by coating a medium resistance rubber layer (522) of about 100,000 Ω · cm on a core metal having a diameter of 9 mm.
The cored bar of the charging roller (160) and a power source (not shown) are electrically connected, and a predetermined bias is applied to the charging roller by the power source. As a result, the peripheral surface of the photoreceptor (140) is uniformly charged to a predetermined polarity and potential.
The charging device used in the present invention is not limited to the contact-type charging device as described above, and may be non-contact. However, since an image forming apparatus in which ozone generated from the charging device is reduced is obtained, the contact-type charging device can be obtained. It is preferable to use a charging device.

Further, in the image forming apparatus of the present invention, an alternating electric field is applied to the charging device. In a DC (direct current) electric field, a large number of O ₃ ⁻ and NO ₃ ⁻ are formed in order to charge the photosensitive member to a negative polarity. The ozone and nitrogen oxides adhere to the photoreceptor and deteriorate the surface of the photoreceptor. In particular, the surface of the photoconductor is hardened and wear increases, and the coefficient of friction decreases, so that external additives are likely to adhere and filming often occurs. For this reason, by applying an alternating electric field on which AC (alternating current) is superimposed, generation of ozone and the like can be suppressed and the photosensitive member can be charged uniformly. In particular, by using an alternating electric field, it is possible to suppress deterioration of the photoreceptor with ozone due to generation of H ₃ O ⁺ having a reverse polarity.

  The shape of the charging member used in the present invention may take any form such as a magnetic brush or a fur brush in addition to the roller, and can be selected according to the specifications and form of the image forming apparatus. In the case of using a magnetic brush, the magnetic brush is composed of various ferrite particles such as Zn—Cu ferrite as a charging member, a non-magnetic conductive sleeve for supporting it, and a magnet roll included therein. In addition, when using a fur brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive core metal. By charging or pasting, it becomes a charging device.

-Tandem type color image forming device-
FIG. 7 is a schematic diagram showing the configuration of the tandem color image forming apparatus of the present invention.
In the tandem type image forming apparatus, as shown in FIG. 7, direct transfer is performed by sequentially transferring the image on each photoconductor (1) to the sheet s conveyed by the sheet conveying belt (3) by the transfer device (2). As shown in FIG. 8, the image on each photosensitive member (1) is once transferred to the intermediate transfer member (4) by the primary transfer device (2), and then transferred to the intermediate transfer member (4). ) There are some indirect transfer systems in which the above image is collectively transferred to the sheet s by the secondary transfer device (5). The transfer device (5) is a transfer conveyance belt, but there are also roller shapes and methods.
Comparing the direct transfer type with the indirect transfer type, the former is a fixing unit on the upstream side of the tandem type image forming apparatus T on which the photoconductors (1) are arranged, and fixing on the downstream side. The apparatus (7) has to be arranged, and there is a drawback that the size is increased in the sheet conveying direction. On the other hand, the latter can set the secondary transfer position relatively freely. The sheet feeding device (6) and the fixing device (7) can be arranged so as to overlap the tandem type image forming apparatus T, and there is an advantage that downsizing is possible.

  In the former, in order not to increase the size in the sheet conveying direction, the fixing device (7) is arranged close to the tandem type image forming apparatus T. For this reason, the fixing device (7) cannot be disposed with a sufficient margin that the sheet s can bend, and an impact when the leading edge of the sheet s enters the fixing device (7) (particularly with a thick sheet). ) And the speed difference between the sheet conveying speed when passing through the fixing device (7) and the sheet conveying speed by the transfer conveying belt, the fixing device (7) tends to affect upstream image formation. . On the other hand, in the latter case, the fixing device (7) can be disposed with a sufficient margin that the sheet s can be bent, and therefore the fixing device (7) can hardly affect the image formation. .

Due to the above, recently, an indirect transfer type among tandem type image forming apparatuses has attracted attention. FIG. 8 is a schematic view showing a configuration of an image forming apparatus having an intermediate transfer member, which is a tandem color image forming apparatus of the present invention.
In this type of color image forming apparatus, as shown in FIG. 8, the transfer residual toner remaining on the photosensitive member (1) after the primary transfer is removed by the photosensitive member cleaning device (8) to remove the photosensitive member ( 1) The surface was cleaned and prepared for another image formation. Further, the transfer residual toner remaining on the intermediate transfer member (4) after the secondary transfer is removed by the intermediate transfer member cleaning device (9) to clean the surface of the intermediate transfer member (4), so as to prepare for image formation again. It was.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 9 shows an embodiment of the present invention and is a schematic diagram showing the configuration of a tandem indirect transfer type image forming apparatus. In the figure, reference numeral (100) is a copying apparatus main body, (200) is a paper feed table on which it is placed, (300) is a scanner mounted on the copying apparatus main body (100), and (400) is an automatic document feeder mounted thereon. (ADF). The copying machine main body (100) is provided with an endless belt-shaped intermediate transfer member (10) in the center.
Then, as shown in FIG. 9, in the example shown in FIG.

In this illustrated example, an intermediate transfer body cleaning device (17) for removing residual toner remaining on the intermediate transfer body (10) after image transfer is provided on the left of the second support roller (15) among the three.
Further, among the three, on the intermediate transfer member (10) stretched between the first support roller (14) and the second support roller (15), yellow, cyan and magenta are arranged along the transport direction. , Black image forming means (18) are arranged side by side to constitute a tandem image forming apparatus (20).
On the tandem image forming apparatus (20), an exposure apparatus (21) is further provided as shown in FIG. On the other hand, a secondary transfer device (22) is provided on the side opposite to the tandem image forming device (20) with the intermediate transfer member (10) interposed therebetween. In the illustrated example, the secondary transfer device (22) includes a secondary transfer belt (24), which is an endless belt, spanned between two rollers (23), and the second transfer device (22) passes through an intermediate transfer member (10). 3 is pressed against the support roller (16), and the image on the intermediate transfer body (10) is transferred to the sheet.

Next to the secondary transfer device (22), a fixing device (25) for fixing the transferred image on the sheet is provided. The fixing device (25) is configured by pressing a pressure roller (27) against a fixing belt (26) which is an endless belt.
The secondary transfer device (22) described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device (25). Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device (22). In such a case, it is difficult to provide this sheet conveying function together.
In the illustrated example, a sheet is placed under such a secondary transfer device (22) and a fixing device (25) so as to record an image on both sides of the sheet in parallel with the tandem image forming device (20). A sheet inverting device (28) for inverting is provided.

Now, when making a copy using this color image forming apparatus, the document is set on the document table (30) of the automatic document feeder (400). Alternatively, the automatic document feeder (400) is opened, a document is set on the contact glass (32) of the scanner (300), and the automatic document feeder (400) is closed and pressed by it.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder (400), the document is transported and moved onto the contact glass (32), and then the other contact glass (32). When a document is set on the scanner, the scanner (300) is immediately driven to travel on the first traveling body (33) and the second traveling body (34). Then, the first traveling body (33) emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body (34) and is reflected by the mirror of the second traveling body (34). Then, the image is placed in the reading sensor (36) through the imaging lens (35) and the content of the original is read.

When a start switch (not shown) is pressed, one of the support rollers (14, 15, 16) is rotationally driven by a drive motor (not shown), and the other two support rollers are driven to rotate, so that the intermediate transfer body (10 ). At the same time, the individual image forming means (18) rotates the photoconductor (40) to form black, yellow, magenta and cyan monochrome images on the photoconductor (40), respectively. Then, along with the conveyance of the intermediate transfer member (10), these monochrome images are sequentially transferred to form a composite color image on the intermediate transfer member (10).
On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers (42) of the paper feed table (200) is selectively rotated, and one of paper feed cassettes (44) provided in multiple stages in the paper bank (43). The sheet is fed out from the sheet, separated one by one by a separation roller (45), put into a sheet feeding path (46), and conveyed by a conveying roller (47) to a sheet feeding path (48) in the copying machine main body (100). Guide and stop against the registration roller (49).

Alternatively, the sheet feeding roller (50) is rotated to feed out the sheets on the manual feed tray (51), separated one by one by the separation roller (52), and placed in the manual sheet feeding path (53). ) And stop.
Then, the registration roller (49) is rotated in time with the composite color image on the intermediate transfer member (10), and the sheet is fed between the intermediate transfer member (10) and the secondary transfer device (22). The image is transferred by the next transfer device (22) and a color image is recorded on the sheet.
The sheet after the image transfer is conveyed by the secondary transfer device (22) and sent to the fixing device (25). The fixing device (25) applies heat and pressure to fix the transferred image, and then the switching claw. It is switched at (55), discharged by the discharge roller (56), and stacked on the discharge tray (57). Alternatively, it is switched by the switching claw (55) and put into the sheet reversing device (28), where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then the paper discharge tray (56) is discharged by the discharge roller (56). 57) Drain up.

On the other hand, the intermediate transfer member (10) after the image transfer is removed by the intermediate transfer member cleaning device (17) to remove residual toner remaining on the intermediate transfer member (10) after the image transfer, and the tandem image forming device (20). To prepare for image formation again.
Here, the registration roller (49) is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.
In the tandem image forming apparatus (20) described above, the individual image forming means (18) includes, for example, a charging device (60), around a drum-shaped photoconductor (40), as shown in FIG. A developing device (61), a primary transfer device (62), a photoconductor cleaning device (63), a charge eliminating device (64), and the like are provided. Although not shown in FIG. 9, (65) is a developer on the developing sleeve, (68) is a stirring paddle, (69) is a partition plate, (71) is a toner concentration sensor, (72) is a developing sleeve, ( 73) a doctor, (75) a cleaning blade, (76) a cleaning brush, (77) a cleaning roller, (78) a cleaning blade, (79) a toner discharge auger, and (80) a driving device. Yes.

~ Process cartridge ~
FIG. 10 is a schematic diagram showing a configuration of a tandem indirect transfer type image forming apparatus including the process cartridge of the present invention. In FIG. 10, a represents the entire process cartridge, b represents a photosensitive member, c represents a charging unit, d represents a developing unit, and e represents a cleaning unit.
In the present invention, at least the photosensitive member b and the developing unit d are integrally combined as a process cartridge among the above-described components such as the photosensitive member b, the charging device unit c, the developing unit d, and the cleaning unit e. The process cartridge is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Hereinafter, “part” means “part by weight” or “%” means “wt%”.
The following Examples 2 to 4, Examples 23 to 32, Examples 43 to 62, and Example 74 are reference examples.

[I] Examples 1 to 12 and Comparative Examples 1 to 4
(Evaluation machine)
Images used in the evaluation were evaluated using any of the following evaluation machines A, B, C, D, and E.

(Evaluation machine A)
Using the tandem Ricoh full-color laser printer IPSiO Color 8000 fixing unit, which has a four-color non-magnetic two-component developing unit and a four-color photoconductor, an oilless fixing unit and tuned the evaluation machine A And evaluated. The printing speed was evaluated by high-speed printing (change from 20 sheets to 50 sheets / min / A4).

(Evaluation machine B)
The tandem Ricoh full color laser printer IPSiO Color 8000, which has a four-color non-magnetic two-component developing unit and a four-color photoconductor, was modified to perform primary transfer onto an intermediate transfer member, and the toner image Evaluation was performed using an evaluation machine B that was tuned by changing to an intermediate transfer system that performs secondary transfer onto a transfer material and improving the fixing unit to an oilless fixing unit. The printing speed was evaluated by high-speed printing (change from 20 sheets to 50 sheets / min / A4).

(Evaluation machine C)
Ricoh's full-color laser copier IMAGIO has a four-color development unit that develops each component of a two-component developer on a drum-shaped photoreceptor, sequentially transfers it to an intermediate transfer member, and transfers all four colors onto a transfer material. The Color 2800 fixing unit was improved to an oilless fixing unit and evaluated using an evaluation machine C that was tuned.

(Evaluation machine D)
Ricoh's full-color laser printer with a four-color developing unit that develops each non-magnetic one-component developer on a belt photoreceptor in sequence, transfers it onto an intermediate transfer member, and transfers all four colors onto a transfer material. The IPSiO Color 5000 fixing unit was improved to an oil-less fixing unit, and evaluation was performed using an evaluation machine D that was tuned with an oil application type.

(Evaluation of two-component developer)
When evaluating an image with a two-component developer, a ferrite carrier having an average particle diameter of 50 μm coated with a silicone resin with an average thickness of 0.3 μm is used as follows, and each color toner 5 is added to 100 parts by weight of the carrier. The developer was prepared by uniformly mixing and charging the parts by weight using a tumbler mixer of the type in which the container rolls and stirs.

(Carrier production)
・ Core material: Cu—Zn ferrite particles (weight average diameter: 35 μm) 5000 parts ・ Coating material: Toluene 450 parts Silicone resin SR2400
(Toray Dow Corning Silicone, 50% nonvolatile content) 450 parts Aminosilane SH6020
(Toray / Dow Corning / Silicone) 10 parts Carbon black 10 parts The above coating material is dispersed with a stirrer for 10 minutes to prepare a coating liquid, and this coating liquid and core material are placed in a fluidized bed. The coating liquid was applied to the core material by applying the coating liquid while forming a swirling flow with the coating. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to obtain the carrier.

(Evaluation item)
1) Carrier spent property Chart of 50% image area of developer charge amount (μc / g) after output of 100,000 sheets while controlling toner density so that image density becomes 1.4 ± 0.2 The amount of change is compared with the initial agent before output. evaluated. The charge amount was measured by the blow-off method.

2) Deterioration fog In an environment where the temperature is 10 ° C. and the humidity is 15%, the degree of toner contamination on the transfer paper upper surface after visualizing the continuous output durability test of 100000 sheets with an image area ratio of 0.5% using each toner is visually observed (loupe ). Evaluations were made from GOOD, ◎, ○, Δ, and ×. ◎ indicates that the toner stain is not observed at all and is in a good state, ○ indicates that the contamination is slightly observed, △ indicates that the contamination is slightly observed, and x indicates that the contamination is not within the allowable range. There is a problem.

3) Toner scattering In an environment of a temperature of 40 ° C. and a humidity of 90%, the toner contamination state in the copier after the 10000 image area ratio 10% chart continuous output durability test using each toner was visually evaluated. ◎ indicates that the toner stain is not observed at all and is in a good state, ○ indicates that the stain is slightly observed, which is not a problem, △ indicates a slight stain is observed, and × indicates that the stain is not within the allowable range. There is a problem.

4) Blocking resistance (environmental preservation)
Weigh 10 g of toner, put it in a 20 ml glass container, tap the glass bottle 100 times, leave it in a thermostatic chamber set at 55 ° C. and 80% humidity for 48 hours, and then adjust the penetration with a penetration meter. It was measured. The toner stored in a low-temperature and low-humidity (10 ° C., 15%) environment was similarly evaluated for penetration, and the value with the lower penetration was employed in a high-temperature and high-humidity and low-temperature and low-humidity environment. From the good one, ◎: 20 mm or more, ◯: 15 mm or more and less than 20 mm, Δ: 10 mm or more to less than 15 mm, x: less than 10 mm.

5) Fixability (hot offset resistance, low temperature fixability)
Ricoh's imagio Neo 450 has been modified to use a belt fixing system, with a solid image and 1.0 ± 0.1mg / mm on plain paper and cardboard transfer paper (Ricoh type 6200 and NBS Ricoh copy printing paper <135>). Fixing evaluation was performed with a toner adhesion amount of cm ² . The fixing test was conducted by changing the temperature of the fixing belt, and the upper limit temperature at which hot offset did not occur on plain paper was defined as the upper limit temperature for fixing. Further, the minimum fixing temperature was measured with a thick paper. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. It is desirable that the fixing upper limit temperature is 200 ° C. or higher and the fixing lower limit temperature is 140 ° C. or lower.

[Synthesis of Titanium-Containing Catalyst (a)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube capable of bubbling in the liquid, 1617 parts of titanium diisopropoxybis (triethanolaminate) and 126 parts of ion-exchanged water are placed in the liquid with nitrogen. Under bubbling, the temperature was gradually raised to 90 ° C., and reaction (hydrolysis) was performed at 90 ° C. for 4 hours to obtain titanium dihydroxybis (triethanolaminate).
In the following examples, the titanium-containing catalyst (a) used in the present invention can be obtained by the same synthesis method.

Example 1
[Synthesis of linear polyester resin]
In a reactor equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 430 parts of PO2 molar adduct of bisphenol A, 300 parts of PO3 molar adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 parts of acid and 2 parts of titanium dihydroxybis (triethanolaminate) were added as a condensation catalyst, and the reaction was carried out for 10 hours while distilling off the water produced at 220 ° C. under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and when the acid value became 5, it took out, cooled to room temperature, and grind | pulverized, and the linear polyester resin (AX1-1) was obtained.
(AX1-1) contained no THF-insoluble matter, and had an acid value of 7, a hydroxyl value of 12, Tg of 60 ° C., Mn of 6940, and Mp of 19100. The ratio of components having a molecular weight of 1500 or less was 1.2%.

[Synthesis of non-linear polyester resin]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 350 parts of EO2 molar adduct of bisphenol A, 326 parts of PO3 molar adduct of bisphenol A, 278 parts of terephthalic acid, 40 parts of phthalic anhydride and condensation As a catalyst, 2 parts of titanium dihydroxybis (triethanolaminate) was added and reacted at 230 ° C. for 10 hours while distilling off the water produced in a nitrogen stream. Next, the reaction is carried out under reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 62 parts of trimellitic anhydride, taken out after reaction for 2 hours under sealed at normal pressure, and cooled to room temperature. To obtain a non-linear polyester resin (AX2-1).
(AX2-1) contained no THF-insoluble matter, and had an acid value of 35, a hydroxyl value of 17, Tg of 69 ° C., Mn of 3920, and Mp of 112010. The ratio of components having a molecular weight of 1500 or less was 0.9%.

[Synthesis of Toner Binder 1]
400 parts of polyester (AX1-1) and 600 parts of polyester (AX2-1) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. for 4 minutes using a steel belt cooler and then pulverized to obtain the toner binder 1 of the present invention.

(Manufacture of toner)
[Black Toner]
Water 1000 parts Phthalocyanine green hydrous cake (solid content 30%) 200 parts Carbon black (MA60 manufactured by Mitsubishi Chemical Corporation) 540 parts Toner binder 1 1200 parts The above raw materials were mixed in a Henschel mixer, and water soaked into the pigment aggregate. A mixture was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch pigment.
Toner binder 1 100 parts Master batch 8 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co.) 2 parts Wax (fatty acid ester wax,
Melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts The above materials were mixed with a mixer, melt-kneaded three or more times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Of black colored particles were obtained. Furthermore, 1.0 wt% of hydrophobic silica having a primary particle size of 10 nm (HDK H2000, Clariant Japan, average particle size of primary particles of 10 nm) is added, mixed with a Henschel mixer, and passed through a sieve having an opening of 50 μm to remove aggregates. As a result, a black toner 1 was obtained.
The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

[Yellow Toner]
600 parts of water
Pigment Yellow 17 hydrous cake (solid content 50%) 1200 parts Toner binder 1 1200 parts The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch pigment.
Toner binder 1 100 parts Master batch 8 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co.) 2 parts Wax (fatty acid ester wax,
Melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts The above materials were mixed with a mixer, then melt-kneaded three or more times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I-type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed to obtain a volume average particle size of 5.5 μm. Of yellow colored particles were obtained. Further, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle size of 10 nm was added, mixed with a Henschel mixer, passed through a sieve having an opening of 50 μm, and the aggregate was removed to obtain yellow toner 1. .
The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

[Magenta toner]
600 parts of water
Pigment Red 57 hydrous cake (solid content 50%) 1200 parts Toner binder 1 1200 parts The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch pigment.
Toner binder 1 100 parts Master batch 8 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co.) 2 parts Wax (fatty acid ester wax,
Melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts The above materials were mixed with a mixer, then melt-kneaded three or more times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and the volume average particle size is 5.5 μm. Of magenta colored particles were obtained. Further, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm was added, mixed with a Henschel mixer, passed through a sieve having an opening of 50 μm, and aggregates were removed to obtain magenta toner 1. .
The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2.

[Cyan toner]
600 parts of water
Pigment Blue 15: 3 Water-containing cake (solid content 50%) 1200 parts Toner binder 1 1200 parts The above raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C., rolled and cooled, and pulverized with a pulverizer to obtain a master batch pigment.
Toner binder 1 100 parts Master batch 8 parts Charge control agent (Bontron E-84 manufactured by Orient Chemical Co.) 2 parts Wax (fatty acid ester wax,
Melting point 83 ° C., viscosity 280 mPa · s (90 ° C.)) 5 parts The above materials were mixed with a mixer, then melt-kneaded three or more times with a two-roll mill, and the kneaded product was rolled and cooled. Thereafter, a collision plate type pulverizer (I type mill; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a jet mill and an air classification (DS classifier; manufactured by Nippon Pneumatic Industry Co., Ltd.) using a swirling flow are performed, and a volume average particle size of 5.5 μm Of cyan colored particles were obtained. Further, 1.0 wt% of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm was added, mixed with a Henschel mixer, passed through a sieve having an opening of 50 μm, and aggregates were removed to obtain magenta toner 1. .
The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Example 2
[Synthesis of linear polyester resin]
A linear polyester resin (AX1-2) was obtained by reacting in the same manner as (AX1-1) in Example 1 except that the polycondensation catalyst was replaced with titanyl bis (triethanolaminate), cooling to room temperature, and pulverizing.
(AX1-2) contained no THF-insoluble matter, and had an acid value of 8, a hydroxyl value of 10, Tg of 60 ° C., Mn of 6820, and Mp of 20180. The ratio of components having a molecular weight of 1500 or less was 1.1%.

[Synthesis of non-linear polyester resin]
A linear polyester resin (AX2-2) was obtained by reacting in the same manner as (AX2-1) in Example 1 except that the polycondensation catalyst was replaced with titanylbis (triethanolaminate), cooling to room temperature, and pulverizing.
(AX2-2) did not contain THF-insoluble matter, and its acid value was 33, hydroxyl value was 14, Tg was 70 ° C., Mn was 4200, and Mp was 11800. The ratio of components having a molecular weight of 1500 or less was 0.8%.

[Synthesis of Toner Binder 2]
500 parts of polyester (AX1-2) and 500 parts of polyester (AX2-2) were powder mixed for 5 minutes with a Henschel mixer to obtain toner binder 2 of the present invention.

(Manufacture of toner)
A toner was manufactured and evaluated in the same manner as the black toner of Example 1 except that the toner binder 2 was used for the toner resin and the master batch resin. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Example 3
[Synthesis of modified polyester resin]
549 parts of bisphenol A propylene oxide 2 mol adduct, 20 parts of bisphenol A propylene oxide 3 mol adduct, 133 parts of bisphenol A ethylene oxide 2 mol adduct in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe , 10 parts of an ethylene oxide 5 mol adduct of phenol novolac (average polymerization degree of about 5), 252 parts of terephthalic acid, 19 parts of isophthalic acid, 10 parts of trimellitic anhydride and 2 parts of titanium dihydroxybis (diethanolamate) as a condensation catalyst The reaction was carried out for 10 hours at 230 ° C. while distilling off the water produced under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and it was made to react until an acid value became 2 or less. Next, 50 parts of trimellitic anhydride was added and reacted at normal pressure for 1 hour. After reacting under reduced pressure of 20 to 40 mmHg and the softening point reached 105 ° C., 20 parts of bisphenol A diglycidyl ether was added, After taking out at a softening point of 150 ° C., cooling to room temperature, and pulverizing, a modified polyester resin (AY1-1) was obtained.
The acid value of (AY1-1) is 52, the hydroxyl value is 16, Tg is 73 ° C., Mn is 1860, Mp is 6550, THF insoluble matter is 32%, and the ratio of components having a molecular weight of 1500 or less is 1.0%. This was used as the toner binder 3.

(Manufacture of toner)
A toner was produced and evaluated in the same manner as the black toner of Example 1 except that the toner binder 3 was used for the toner resin and the master batch resin. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Example 4
[Synthesis of non-linear polyester resin]
132 parts of bisphenol A propylene oxide 2-mole adduct, 371 parts of bisphenol A propylene oxide 3-mole adduct, 20 parts of bisphenol A ethylene oxide 2-mole adduct, 125 parts of propylene oxide 5 mol adduct of phenol novolak (average degree of polymerization about 5), 201 parts of terephthalic acid, 25 parts of maleic anhydride, 35 parts of dimethyl terephthalic acid ester and 2 parts of titanyl bis (triethanolaminate) as a condensation catalyst The reaction was carried out for 10 hours while distilling off the water produced at 230 ° C. under a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 65 parts of trimellitic anhydride, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. To obtain a non-linear polyester resin (AX2-3).
The non-linear polyester resin (AX2-3) has a softening point of 144 ° C., an acid value of 30, a hydroxyl value of 16, Tg of 59 ° C., Mn of 1410, Mp of 4110, a THF insoluble content of 27%, and a molecular weight of 1500 or less. The ratio of this component was 1.0%, and this was used as the toner binder 4.

(Manufacture of toner)
A toner was manufactured and evaluated in the same manner as the black toner of Example 1 except that the toner binder 4 was used for the toner resin and the master batch resin. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Example 5
[Synthesis of non-linear polyester resin]
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 410 parts of bisphenol A propylene oxide 2 mol adduct, 270 parts of bisphenol A propylene oxide 3 mol adduct, 110 parts terephthalic acid, 125 parts isophthalic acid, 15 parts of maleic anhydride and 2 parts of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted at 220 ° C. for 10 hours while distilling off the water produced under a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value becomes 2 or less, it is cooled to 180 ° C., 25 parts of trimellitic anhydride is added, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. By pulverizing, a non-linear polyester resin (AX2-4) was obtained.
(AX2-4) contained no THF-insoluble matter, and had an acid value of 18, a hydroxyl value of 37, Tg of 62 ° C., Mn of 2130, and Mn of 5350. The ratio of components having a molecular weight of 1500 or less was 1.3%.

[Synthesis of modified polyester resin]
317 parts of bisphenol A ethylene oxide 2-mole adduct, 57 parts of bisphenol A propylene oxide 2-mole adduct, 298 parts of bisphenol A propylene oxide 3-mole adduct, 75 parts of propylene oxide 5 mol adduct of phenol novolak (average degree of polymerization about 5), 30 parts of isophthalic acid, 157 parts of terephthalic acid, 27 parts of maleic anhydride and 2 parts of titanium dihydroxybis (triethanolaminate) as a condensation catalyst The reaction was carried out for 10 hours while distilling off the water produced at 230 ° C. under a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, the mixture was cooled to 180 ° C., and then 68 parts of trimellitic anhydride was added and reacted under normal pressure for 1 hour, and then 20 to 40 mmHg. When the softening point is 120 ° C by reaction under reduced pressure, 25 parts of bisphenol A diglycidyl ether is added, taken out at a softening point of 155 ° C, cooled to room temperature, pulverized, and modified polyester resin (AY1-2) is obtained. Obtained.
The acid value of (AY1-2) was 11, the hydroxyl value was 27, Tg was 60 ° C., Mn was 3020, Mp was 6030, and the THF-insoluble content was 35%. The ratio of components having a molecular weight of 1500 or less was 1.1%.

[Synthesis of Toner Binder 5]
500 parts of (AX2-3) and 500 parts of (AY1-2) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. for 4 minutes using a steel belt cooler and pulverized to obtain toner binder 5 of the present invention.

(Manufacture of toner)
A toner was produced and evaluated in the same manner as the black toner of Example 1 except that the toner binder 5 was used for the toner resin and the master batch resin. The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Example 6
Evaluation was performed in the same manner as in Example 1 except that the black toner 1 of Example 1 was manufactured by changing the following external additive mixing method to wet.
A monopump containing 10 parts of black colored particles having a volume average particle diameter of 5.5 μm and 2 parts of hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm in water containing 0.1% of a surfactant. Dispersed and mixed. While monitoring with a fluorescent X-ray report, the toner was taken out of water so that the amount of silica adhered was 1 wt%, and passed through a sieve having an opening of 50 μm to remove aggregates, thereby obtaining a black toner.
The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Example 7
Evaluation was performed in the same manner as in Example 1 except that the black toner 1 of Example 1 was manufactured by changing to the following external additive mixing method.
Black toner was further obtained by mixing 0.4 part of zinc stearate with black toner 1 using a Henschel mixer, and again passing through a sieve having an opening of 50 μm to remove aggregates.
The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Example 8
Evaluation was performed in the same manner as in Example 1 except that the black toner 1 of Example 1 was manufactured by changing to the following external additive mixing method.
Black toner was obtained by further mixing 0.5 wt% of titanium oxide (STM-150AI, Taker, average particle size of primary particles 15 nm) with black toner 1 and passing through a sieve having an opening of 50 μm to remove aggregates. .
The toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Example 9
Evaluation was performed in the same manner as in Example 1 except that the toner was a chemical toner manufactured as follows.
~ Synthesis of organic fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, 110 butyl acrylate Parts and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 3 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 70 ° C. for 5 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 75 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 60 ° C., and the weight average molecular weight was 110,000.

-Adjustment of aqueous phase-
Production Example 2
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of dodecyl diphenyl ether disulfonate ((Eleminol MON-7): Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. As a result, a milky white liquid was obtained. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reactor equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 430 parts of PO2 molar adduct of bisphenol A, 300 parts of PO3 molar adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 parts of acid and 2 parts of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted at 200 ° C. for 8 hours while distilling off water produced under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and when the acid value became 7, it took out, cooled to room temperature, and grind | pulverized, and the low molecular polyester resin 1 was obtained.
The low molecular weight polyester resin 1 did not contain a THF-insoluble component, and its acid value was 9, the hydroxyl value was 12, Tg was 52 ° C., Mn was 4820, and Mp was 17000. The ratio of components having a molecular weight of 1500 or less was 0.8%.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 7 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

~ Synthesis of ketimine ~
Production Example 5
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

~ Synthesis of master batch (MB) ~
Production Example 6
600 parts of water, Pigment Blue 15: 3 water-containing cake (solid content 50%) and 1200 parts of polyester resin are added and mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), and the mixture is used at 120 ° C. for 45 minutes using two rolls. After kneading, rolling and cooling and pulverization with a pulverizer gave [Masterbatch 1].

~ Creation of oil phase ~
Production Example 7
In a container in which a stir bar and a thermometer were set, 378 parts of [Low molecular weight polyester 1], 100 parts of Carnauba WAX, and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. The pigment and WAX were dispersed under the conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
Production Example 8
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, and [Ketimine Compound 1] 2.9 parts were put in a container and mixed with a TK homomixer (manufactured by Tokushu Kika) at 5000 rpm for 2 minutes. Thereafter, 1200 parts of [Aqueous Phase 1] was added to the container, and mixed with a TK homomixer at a rotational speed of 13000 rpm for 25 minutes to obtain [Emulsified Slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

~ Washing⇒Drying ~
Production Example 9
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
1: 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
100 parts of a 10% aqueous sodium hydroxide solution was added to a 2: 1 filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 30 minutes), and then filtered under reduced pressure.
100 parts of 10% hydrochloric acid was added to the 3: 2 filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
300 parts of ion-exchanged water was added to the 4: 3 filter cake, mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered twice to obtain [Filter cake 1].
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer.
Thereafter, the following fluorine compound (2) is mixed in an aqueous solvent soda containing 1 wt% concentration so that the following fluorine compound (2) is 0.1 wt. After adhering (bonding), it was dried at 45 ° C. for 48 hours in a circulating drier, and further dried on a shelf at 30 ° C. for 10 hours. Thereafter, sieved with a mesh of 75 μm, [Toner Base Particle 1] was obtained.
Fluorine compound (2)

その後、［トナー母体粒子１］１００部、一次粒子径１０ｎｍの疎水性シリカ（HDK H2000、クラリアントジャパン）をヘンシェルミキサー（三井鉱山社製 ＦＭ２０Ｃ）にて混合してトナーを得た。混合条件は、周速３０ｍ／ｓｅｃで、１２０秒回転、６０秒回転停止、のセットを３回繰り返して混合してトナーを得た。
得られたトナーの物性は表１、評価結果は表２に示した。評価機は評価機Ａを用いた。

Thereafter, 100 parts of [toner base particle 1] and hydrophobic silica (HDK H2000, Clariant Japan) having a primary particle diameter of 10 nm were mixed with a Henschel mixer (FM20C manufactured by Mitsui Mining Co., Ltd.) to obtain a toner. The mixing conditions were a circumferential speed of 30 m / sec, a set of 120 second rotation and 60 second rotation stop was repeated three times to mix and obtain a toner.
The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Examples 10-12
In Example 1, evaluation was performed in the same manner as in Example 1 except that the black toner described in Example 1 was used and the evaluation machine was evaluated using the evaluation machine B, the evaluation machine C, and the evaluation machine D, respectively. The evaluation results are shown in Table 2.

Comparative Example 1
A toner was produced and evaluated in the same manner as the black toner of Example 1 except that the binder resin used in the black toner of Example 1 was changed to the following resin H2.
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 7 hours at normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride to the reaction vessel at 180 ° C at normal pressure. By reacting for 3 hours, a polyester resin H2 was obtained. Polyester resin H2 had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, a Tg of 43 ° C., and an acid value of 25. As a reaction catalyst, 1 part of dibutyltin was mixed and used.
The obtained toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Comparative Example 2
The black toner of Example 1 was manufactured and evaluated in the same manner as the black toner of Example 1, except that the particle size, particle size distribution, fine powder, and sparse powder content were classified as shown in Table 1. The obtained toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Comparative Example 3
The black toner of Example 1 was manufactured and evaluated in the same manner as the black toner of Example 1, except that the particle size, particle size distribution, fine powder, and sparse powder content were classified as shown in Table 1. The obtained toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

Comparative Example 4
The black toner of Example 1 was manufactured and evaluated in the same manner as the black toner of Example 1, except that the particle size, particle size distribution, fine powder, and sparse powder content were classified as shown in Table 1. The obtained toner physical properties are shown in Table 1, and the evaluation results are shown in Table 2. Evaluation machine A was used as the evaluation machine.

[II] Examples 13 to 72 and Comparative Examples 5 to 24
(Synthesis of toner binder A)
[Synthesis of linear polyester resin]
In a reactor equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 430 parts of PO2 molar adduct of bisphenol A, 300 parts of PO3 molar adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 parts of acid and 2 parts of titanium dihydroxybis (triethanolaminate) were added as a condensation catalyst, and the reaction was carried out for 10 hours while distilling off the water produced at 220 ° C. under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and when the acid value became 5, it took out, cooled to room temperature, and grind | pulverized, and the linear polyester resin (AX1-1) was obtained.
(AX1-1) contained no THF-insoluble matter, and had an acid value of 7, a hydroxyl value of 12, Tg of 60 ° C., Mn of 6940, and Mp of 19100. The ratio of components having a molecular weight of 1500 or less was 1.2%.

[Synthesis of non-linear polyester resin]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 350 parts of EO2 molar adduct of bisphenol A, 326 parts of PO3 molar adduct of bisphenol A, 278 parts of terephthalic acid, 40 parts of phthalic anhydride and condensation As a catalyst, 2 parts of titanium dihydroxybis (triethanolaminate) was added and reacted at 230 ° C. for 10 hours while distilling off the water produced in a nitrogen stream. Next, the reaction is carried out under reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 62 parts of trimellitic anhydride, taken out after reaction for 2 hours under sealed at normal pressure, and cooled to room temperature. To obtain a non-linear polyester resin (AX2-1).
(AX2-1) contained no THF-insoluble matter, and its acid value was 35, the hydroxyl value was 17, Tg was 69 ° C., Mn was 3920, and Mp was 11200. The ratio of components having a molecular weight of 1500 or less was 0.9%.

[Synthesis of Toner Binder A]
400 parts of polyester (AX1-1) and 600 parts of polyester (AX2-1) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. for 4 minutes using a steel belt cooler and then pulverized to obtain toner binder A of the present invention.

(Synthesis of toner binder B)
[Synthesis of linear polyester resin]
A linear polyester resin (AX1-2) is obtained by reacting in the same manner as (AX1-1) in the synthesis of toner binder A except that the polycondensation catalyst is replaced with titanylbis (triethanolaminate), cooling to room temperature, and pulverizing. It was.
(AX1-2) contained no THF-insoluble matter, and had an acid value of 8, a hydroxyl value of 10, Tg of 60 ° C., Mn of 6820, and Mp of 20180. The ratio of components having a molecular weight of 1500 or less was 1.1%.

[Synthesis of non-linear polyester resin]
Except for replacing the polycondensation catalyst with titanyl bis (triethanolaminate), the reaction is carried out in the same manner as (AX2-1) in the synthesis of toner binder A, cooled to room temperature, and pulverized to obtain a linear polyester resin (AX2-2). It was.
(AX2-2) did not contain THF-insoluble matter, and its acid value was 33, hydroxyl value was 14, Tg was 70 ° C., Mn was 4200, and Mp was 11800. The ratio of components having a molecular weight of 1500 or less was 0.8%.

[Synthesis of Toner Binder B]
500 parts of polyester (AX1-2) and 500 parts of polyester (AX2-2) were powder mixed for 5 minutes in a Henschel mixer to obtain toner binder B of the present invention.

(Synthesis of toner binder C)
[Synthesis of linear polyester resin for comparison]
The reaction was carried out in the same manner as (AX1-1) in the synthesis of toner binder A, except that the polycondensation catalyst was replaced with titanium tetraisopropoxide. Since the reaction was stopped in the middle due to catalyst deactivation and the problem that the generated water could not be distilled occurred, 2 parts of titanium tetraisopropoxide was added four times during the reaction, and a comparative linear polyester resin (CAX1) was added. -1) was obtained.
(CAX1-1) contained no THF-insoluble matter, and had an acid value of 7, a hydroxyl value of 12, Tg of 58 ° C., Mn of 6220, and Mp of 18900. The ratio of components having a molecular weight of 1500 or less was 2.2%.

[Synthesis of non-linear polyester resin for comparison]
The reaction was carried out in the same manner as (AX2-1) in the synthesis of toner binder A, except that the polycondensation catalyst was replaced with titanium tetraisopropoxide. The reaction was allowed to proceed for 16 hours under normal pressure and for 8 hours under reduced pressure. Since the reaction rate was slow, 2 parts of titanium tetrapropoxide were added three times during the reaction to obtain a comparative non-linear polyester resin (CAX2-1).
(CAX2-1) contained no THF-insoluble matter, and its acid value was 34, the hydroxyl value was 16, Tg was 68 ° C., Mn was 3420, and Mp was 12100. The ratio of components having a molecular weight of 1500 or less was 2.1%.

[Synthesis of Toner Binder C]
400 parts of polyester (CAX1-1) and 600 parts of polyester (CAX2-1) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. for 4 minutes using a steel belt cooler and pulverized to obtain a comparative toner binder C. The toner binder C was a resin having a strong purple brown color.

(Example 13)
100 parts of toner binder A of the present invention, 5 parts of carnauba wax [carnauba wax C1, melting point 84 ° C., manufactured by Kato Yoko Co., Ltd.] and 4 parts of yellow pigment [toner yellow HG VP2155 manufactured by Clariant Co., Ltd.] and zinc salicylate [Orient Three parts of Bontron E-84 manufactured by Chemical Industry Co., Ltd. were premixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.] and then mixed with a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Kneaded. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and the particle size D50 was 8 μm. Toner particles were obtained. Subsequently, 0.5 part of colloidal silica [Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.] was mixed with 100 parts of toner particles by a sample mill to obtain a toner (T13).

(Example 14)
From zinc salicylate [Orient Chemical Industries, Ltd. Bontron E-84] to quaternary ammonium salts [Orient Chemical Industries, Ltd. Bontron P-51] and colloidal silica [Nippon Aerosil Co., Ltd. Aerosil R972] A toner (T14) was obtained in the same manner as in Example 13 except for changing to [W30 Chemical H30TA].

(Example 15)
Example 13 except that salicylic acid zinc salt [Bontron E-84, manufactured by Orient Chemical Industries, Ltd.] is changed to bis [1- (5-chloro-2-hydroxyphenylazo-2-naphtholato) chromium (III) acid. Similarly, toner (T15) was obtained.

(Example 16)
From salicylic acid zinc salt [Orient Chemical Industries, Ltd. Bontron E-84] to Nigrosine [Orient Chemical Industries, Ltd. Nigrosine Base EX], and colloidal silica [Nippon Aerosil Co., Ltd. Aerosil R972] [Wacker Chemical, Inc.] A toner (T16) was obtained in the same manner as in Example 13 except that the toner was changed to [H30TA].

(Example 17)
A toner (T17) was obtained in the same manner as in Example 13, except that the salicylic acid zinc salt [Bontron E-84 manufactured by Orient Chemical Co., Ltd.] was changed to the fluorine compound [Copy Charge NX VP 434 manufactured by Clariant Co., Ltd.]. .

(Example 18)
Toner (T18) was prepared in the same manner as in Example 13 except that zinc salicylate [Bontron E-84 manufactured by Orient Chemical Industry Co., Ltd.] was changed to perfluoroalkyltrimethylammonium iodide [FT-310 manufactured by Neos Co., Ltd.]. Obtained.

(Example 19)
Zinc salicylate [Orient Chemical Industries, Ltd. Bontron E-84] to quaternary ammonium salt-containing styrene acrylic copolymer [Fujikura Kasei Co., Ltd. FCA-77PR], and colloidal silica [Nippon Aerosil Co., Ltd.] A toner (T19) was obtained in the same manner as in Example 13 except that Aerosil R972] was changed to [W30 Chemical H30TA].

(Example 20)
A toner (T20) was obtained in the same manner as in Example 13 except that salicylic acid zinc salt [Bontron E-84 manufactured by Orient Chemical Industry Co., Ltd.] was changed to Cr azo dye [CCA-7 manufactured by Zeneca Co., Ltd.].

(Example 21)
A toner (T21) was obtained in the same manner as in Example 13 except that zinc salicylate [Bontron E-84 manufactured by Orient Chemical Industry Co., Ltd.] was changed to Fe azo dye [T-77 manufactured by Hodogaya Chemical Co., Ltd.]. .

(Example 22)
A toner (T22) was obtained in the same manner as in Example 13 except that the salicylic acid zinc salt [Bontron E-84 manufactured by Orient Chemical Co., Ltd.] was changed to polyhydroxyalkanoate. An example of the production method of polyhydroxyalkanoate is shown below.
[Polyhydroxyalkanoate production method]
Agar colonies were inoculated into 200 mL of a medium containing 0.5% polypeptone and 0.1% 5-phenylsulfanylvaleric acid, and cultured in a 500 mL shake flask at 30 ° C. for 30 hours. After culturing, the cells were harvested by centrifugation, washed with methanol, and lyophilized. After weighing the dried cells, acetone was added and the polymer was extracted by stirring at room temperature (about 23 ° C.) for 72 hours. The acetone from which the polymer was extracted was filtered and concentrated with an evaporator, and then the precipitated and solidified portion was collected with cold methanol and dried under reduced pressure to obtain the desired polymer. The weight of the dried cells was 215 mg, and the weight of the obtained polymer was 76 mg.

(Example 23)
A toner (T23) was obtained in the same manner as in Example 13 except that the toner binder A was changed to the toner binder B.

(Example 24)
A toner (T24) was obtained in the same manner as in Example 14 except that the toner binder A was changed to the toner binder B.

(Example 25)
A toner (T25) was obtained in the same manner as in Example 15 except that the toner binder A was changed to the toner binder B.

(Example 26)
A toner (T26) was obtained in the same manner as in Example 16 except that the toner binder A was changed to the toner binder B.

(Example 27)
A toner (T27) was obtained in the same manner as in Example 17 except that the toner binder A was changed to the toner binder B.

(Example 28)
A toner (T28) was obtained in the same manner as in Example 18 except that the toner binder A was changed to the toner binder B.

(Example 29)
A toner (T29) was obtained in the same manner as in Example 19 except that the toner binder A was changed to the toner binder B.

(Example 30)
A toner (T30) was obtained in the same manner as in Example 20 except that the toner binder A was changed to the toner binder B.

(Example 31)
A toner (T31) was obtained in the same manner as in Example 21 except that the toner binder A was changed to the toner binder B.

(Example 32)
A toner (T32) was obtained in the same manner as in Example 22 except that the toner binder A was changed to the toner binder B.

(Example 33)
From 3 parts of zinc salicylic acid [Orient Chemical Industries, Ltd. Bontron E-84], 3 parts of salicylic acid zinc salt [Orient Chemical Industries, Ltd. Bontron E-84] and bis [1- (5-chloro-2- Toner (T33) was obtained in the same manner as in Example 13 except that the amount was changed to 2 parts of hydroxyphenylazo-2-naphtholato) chromium (III) acid.

(Example 34)
Quaternary ammonium salt [Orient Chemical Industries, Ltd. Bontron P-51] 3 parts to quaternary ammonium salt [Orient Chemical Industries, Ltd. Bontron P-51] 3 parts and Nigrosine [Orient Chemical Industries, Ltd. Nigrosine Base EX] A toner (T34) was obtained in the same manner as in Example 14 except for changing to 2 parts.

(Example 35)
From 3 parts of bis [1- (5-chloro-2-hydroxyphenylazo-2-naphtholato) chromium (III) acid, bis [1- (5-chloro-2-hydroxyphenylazo-2-naphtholato) chromium (III ) A toner (T35) was obtained in the same manner as in Example 15 except that 3 parts of acid and 2 parts of salicylic acid zinc salt [Bontron E-84 manufactured by Orient Chemical Industry Co., Ltd.] were used.

(Example 36)
Nigrosine [Orient Chemical Industry Co., Ltd. Nigrosine Base EX] 3 parts, Nigrosine [Orient Chemical Industry Co., Ltd. Nigrosine Base EX] 3 parts and quaternary ammonium salt [Orient Chemical Industry Co., Ltd. Bontron P-51] A toner (T36) was obtained in the same manner as in Example 16 except for changing to 2 parts.

(Example 37)
Fluorine compound [Clariant Co., Ltd., Copy Charge NX VP 434] 3 parts, Fluorine compound [Clariant Co., Ltd., Copy Charge NX VP 434] 3 parts and salicylic acid zinc salt [Orient Chemical Industries, Ltd. Bontron E-84 A toner (T37) was obtained in the same manner as in Example 17 except for changing to 2 parts.

(Example 38)
From 3 parts of perfluoroalkyltrimethylammonium iodide [FT-310 made by Neos Co., Ltd.], 3 parts of perfluoroalkyltrimethylammonium iodide [FT-310 made by Neos Co., Ltd.] and zinc salicylic acid [Orient Chemical Co., Ltd. made] Bontron E-84] A toner (T38) was obtained in the same manner as in Example 18 except for changing to 2 parts.

(Example 39)
From 3 parts of quaternary ammonium salt-containing styrene acrylic copolymer [FCA-77PR manufactured by Fujikura Kasei Co., Ltd.] 3 parts and 4 of quaternary ammonium salt-containing styrene acrylic copolymer [FCA-77PR manufactured by Fujikura Kasei Co., Ltd.] A toner (T39) was obtained in the same manner as in Example 19 except that the amount was changed to 2 parts of a quaternary ammonium salt [Bontron P-51, manufactured by Orient Chemical Co., Ltd.].

(Example 40)
From 3 parts of Cr azo dye [CCA-7 manufactured by Zeneca Co., Ltd.], 3 parts of Cr azo dye [CCA-7] manufactured by Zeneca Co., Ltd. and zinc salicylic acid [Bontron E-84 manufactured by Orient Chemical Co., Ltd.] 2 A toner (T40) was obtained in the same manner as in Example 20 except that the amount of the toner was changed.

(Example 41)
3 parts of Fe azo dye [T-77 made by Hodogaya Chemical Co., Ltd.], 3 parts of Fe azo dye [T-77 made by Hodogaya Chemical Co., Ltd.] and Bontron E-84 made by zinc salicylate [Orient Chemical Co., Ltd.] A toner (T41) was obtained in the same manner as in Example 21 except that the amount was changed to 2 parts.

(Example 42)
Toner (T42) was prepared in the same manner as in Example 22 except that 3 parts of polyhydroxyalkanoate was changed to 3 parts of polyhydroxyalkanoate and 2 parts of salicylic acid zinc salt [Bontron E-84 manufactured by Orient Chemical Co., Ltd.] Obtained.

(Comparative Example 5)
A toner (T5 ′) was obtained in the same manner as in Example 13 except that the toner binder A was changed to the toner binder C.

(Comparative Example 6)
A toner (T6 ′) was obtained in the same manner as in Example 14 except that the toner binder A was changed to the toner binder C.

(Comparative Example 7)
A toner (T7 ′) was obtained in the same manner as in Example 15 except that the toner binder A was changed to the toner binder C.

(Comparative Example 8)
A toner (T8 ′) was obtained in the same manner as in Example 16 except that the toner binder A was changed to the toner binder C.

(Comparative Example 9)
A toner (T9 ′) was obtained in the same manner as in Example 17 except that the toner binder A was changed to the toner binder C.

(Comparative Example 10)
A toner (T10 ′) was obtained in the same manner as in Example 18 except that the toner binder A was changed to the toner binder C.

(Comparative Example 11)
A toner (T11 ′) was obtained in the same manner as in Example 19 except that the toner binder A was changed to the toner binder C.

(Comparative Example 12)
A toner (T12 ′) was obtained in the same manner as in Example 20 except that the toner binder A was changed to the toner binder C.

(Comparative Example 13)
A toner (T13 ′) was obtained in the same manner as in Example 21 except that the toner binder A was changed to the toner binder C.

(Comparative Example 14)
A toner (T14 ′) was obtained in the same manner as in Example 22 except that the toner binder A was changed to the toner binder C.

(Synthesis of toner binder D)
[Synthesis of modified polyester resin]
549 parts of bisphenol A propylene oxide 2 mol adduct, 20 parts of bisphenol A propylene oxide 3 mol adduct, 133 parts of bisphenol A ethylene oxide 2 mol adduct in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe , 10 parts of an ethylene oxide 5 mol adduct of phenol novolac (average polymerization degree of about 5), 252 parts of terephthalic acid, 19 parts of isophthalic acid, 10 parts of trimellitic anhydride and 2 parts of titanium dihydroxybis (diethanolamate) as a condensation catalyst The reaction was carried out for 10 hours at 230 ° C. while distilling off the water produced under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and it was made to react until an acid value became 2 or less. Next, 50 parts of trimellitic anhydride was added and reacted at normal pressure for 1 hour. After reacting under reduced pressure of 20 to 40 mmHg and the softening point reached 105 ° C., 20 parts of bisphenol A diglycidyl ether was added, After taking out at a softening point of 150 ° C., cooling to room temperature, and pulverizing, a modified polyester resin (AY1-1) was obtained.
The acid value of (AY1-1) is 52, the hydroxyl value is 16, Tg is 73 ° C., Mn is 1860, Mp is 6550, THF insoluble matter is 32%, and the ratio of components having a molecular weight of 1500 or less is 1.0%. This was used as a toner binder (D).

(Synthesis of toner binder E)
[Synthesis of modified polyester resin]
A modified polyester resin for comparison (CAY1-2) was obtained by reacting in the same manner as in Example 15 except that the polycondensation catalyst was replaced with titanium tetrabutoxide.
(CAY1-2) has a softening point of 150 ° C., an acid value of 53, a hydroxyl value of 17, Tg of 71 ° C., Mn of 1660, Mp of 6340, a THF insoluble content of 34%, and a ratio of components having a molecular weight of 1500 or less. This was 3.1%, and this was used as a toner binder (E).

(Synthesis of toner binder F)
[Synthesis of non-linear polyester resin]
132 parts of bisphenol A propylene oxide 2-mole adduct, 371 parts of bisphenol A propylene oxide 3-mole adduct, 20 parts of bisphenol A ethylene oxide 2-mole adduct, 125 parts of propylene oxide 5 mol adduct of phenol novolak (average degree of polymerization about 5), 201 parts of terephthalic acid, 25 parts of maleic anhydride, 35 parts of dimethyl terephthalic acid ester and 2 parts of titanyl bis (triethanolaminate) as a condensation catalyst The reaction was carried out for 10 hours while distilling off the water produced at 230 ° C. under a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 65 parts of trimellitic anhydride, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. To obtain a non-linear polyester resin (AX2-3).
The non-linear polyester resin (AX2-3) has a softening point of 144 ° C., an acid value of 30, a hydroxyl value of 16, Tg of 59 ° C., Mn of 1410, Mp of 4110, a THF insoluble content of 27%, and a molecular weight of 1500 or less. The ratio of this component was 1.0%, and this was used as the toner binder (F).

(Synthesis of toner binder G)
[Synthesis of non-linear polyester resin]
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 410 parts of bisphenol A propylene oxide 2 mol adduct, 270 parts of bisphenol A propylene oxide 3 mol adduct, 110 parts terephthalic acid, 125 parts isophthalic acid, 15 parts of maleic anhydride and 2 parts of titanium dihydroxybis (triethanolaminate) as a condensation catalyst were added and reacted at 220 ° C. for 10 hours while distilling off the water produced under a nitrogen stream. Next, the reaction is carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value becomes 2 or less, it is cooled to 180 ° C., 25 parts of trimellitic anhydride is added, taken out after reaction for 2 hours under normal pressure sealing, and cooled to room temperature. By pulverizing, a non-linear polyester resin (AX2-4) was obtained.
(AX2-4) contained no THF-insoluble matter, and had an acid value of 18, a hydroxyl value of 37, Tg of 62 ° C., Mn of 2130, and Mn of 5350. The ratio of components having a molecular weight of 1500 or less was 1.3%.

[Synthesis of modified polyester resin]
317 parts of bisphenol A ethylene oxide 2-mole adduct, 57 parts of bisphenol A propylene oxide 2-mole adduct, 298 parts of bisphenol A propylene oxide 3-mole adduct, 75 parts of propylene oxide 5 mol adduct of phenol novolak (average degree of polymerization about 5), 30 parts of isophthalic acid, 157 parts of terephthalic acid, 27 parts of maleic anhydride and 2 parts of titanium dihydroxybis (triethanolaminate) as a condensation catalyst The reaction was carried out for 10 hours while distilling off the water produced at 230 ° C. under a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, the mixture was cooled to 180 ° C., and then 68 parts of trimellitic anhydride was added and reacted under normal pressure for 1 hour, and then 20 to 40 mmHg. When the softening point is 120 ° C by reaction under reduced pressure, 25 parts of bisphenol A diglycidyl ether is added, taken out at a softening point of 155 ° C, cooled to room temperature, pulverized, and modified polyester resin (AY1-2) is obtained. Obtained. The acid value of (AY1-2) was 11, the hydroxyl value was 27, Tg was 60 ° C., Mn was 3020, Mp was 6030, and the THF-insoluble content was 35%. The ratio of components having a molecular weight of 1500 or less was 1.1%.

[Synthesis of Toner Binder G]
500 parts of polyester (AX2-3) and 500 parts of polyester (AY1-2) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. for 4 minutes using a steel belt cooler and then pulverized to obtain the toner binder (G) of the present invention.

(Example 43)
A toner (T43) was obtained in the same manner as in Example 13 except that the toner binder A was changed to the toner binder D.

(Example 44)
A toner (T44) was obtained in the same manner as in Example 14 except that the toner binder A was changed to the toner binder D.

(Example 45)
A toner (T45) was obtained in the same manner as in Example 15 except that the toner binder A was changed to the toner binder D.

(Example 46)
A toner (T46) was obtained in the same manner as in Example 16 except that the toner binder A was changed to the toner binder D.

(Example 47)
A toner (T47) was obtained in the same manner as in Example 17 except that the toner binder A was changed to the toner binder D.

(Example 48)
A toner (T48) was obtained in the same manner as in Example 18 except that the toner binder A was changed to the toner binder D.

(Example 49)
A toner (T49) was obtained in the same manner as in Example 19 except that the toner binder A was changed to the toner binder D.

(Example 50)
A toner (T50) was obtained in the same manner as in Example 20 except that the toner binder A was changed to the toner binder D.

(Example 51)
A toner (T51) was obtained in the same manner as in Example 21 except that the toner binder A was changed to the toner binder D.

(Example 52)
A toner (T52) was obtained in the same manner as in Example 22 except that the toner binder A was changed to the toner binder D.

(Example 53)
A toner (T53) was obtained in the same manner as in Example 13 except that the toner binder A was changed to the toner binder F.

(Example 54)
A toner (T54) was obtained in the same manner as in Example 14 except that the toner binder A was changed to the toner binder F.

(Example 55)
A toner (T55) was obtained in the same manner as in Example 15 except that the toner binder A was changed to the toner binder F.

(Example 56)
A toner (T56) was obtained in the same manner as in Example 16 except that the toner binder A was changed to the toner binder F.

(Example 57)
A toner (T57) was obtained in the same manner as in Example 17 except that the toner binder A was changed to the toner binder F.

(Example 58)
A toner (T58) was obtained in the same manner as in Example 18 except that the toner binder A was changed to the toner binder F.

(Example 59)
A toner (T59) was obtained in the same manner as in Example 19 except that the toner binder A was changed to the toner binder F.

(Example 60)
A toner (T60) was obtained in the same manner as in Example 20 except that the toner binder A was changed to the toner binder F.

(Example 61)
A toner (T61) was obtained in the same manner as in Example 21 except that the toner binder A was changed to the toner binder F.

(Example 62)
A toner (T62) was obtained in the same manner as in Example 22 except that the toner binder A was changed to the toner binder F.

(Example 63)
A toner (T63) was obtained in the same manner as in Example 13 except that the toner binder A was changed to the toner binder G.

(Example 64)
A toner (T64) was obtained in the same manner as in Example 14 except that the toner binder A was changed to the toner binder G.

(Example 65)
A toner (T65) was obtained in the same manner as in Example 15 except that the toner binder A was changed to the toner binder G.

Example 66
A toner (T66) was obtained in the same manner as in Example 16 except that the toner binder A was changed to the toner binder G.

(Example 67)
A toner (T67) was obtained in the same manner as in Example 17 except that the toner binder A was changed to the toner binder G.

Example 68
A toner (T68) was obtained in the same manner as in Example 18 except that the toner binder A was changed to the toner binder G.

(Example 69)
A toner (T69) was obtained in the same manner as in Example 19 except that the toner binder A was changed to the toner binder G.

(Example 70)
A toner (T70) was obtained in the same manner as in Example 20 except that the toner binder A was changed to the toner binder G.

(Example 71)
A toner (T71) was obtained in the same manner as in Example 21 except that the toner binder A was changed to the toner binder G.

(Example 72)
A toner (T72) was obtained in the same manner as in Example 22 except that the toner binder A was changed to the toner binder G.

(Comparative Example 15)
A toner (T15 ′) was obtained in the same manner as in Example 13 except that the toner binder A was changed to the toner binder E.

(Comparative Example 16)
A toner (T16 ′) was obtained in the same manner as in Example 14 except that the toner binder A was changed to the toner binder E.

(Comparative Example 17)
A toner (T17 ′) was obtained in the same manner as in Example 15 except that the toner binder A was changed to the toner binder E.

(Comparative Example 18)
A toner (T18 ′) was obtained in the same manner as in Example 16 except that the toner binder A was changed to the toner binder E.

(Comparative Example 19)
A toner (T19 ′) was obtained in the same manner as in Example 17 except that the toner binder A was changed to the toner binder E.

(Comparative Example 20)
A toner (T20 ′) was obtained in the same manner as in Example 18 except that the toner binder A was changed to the toner binder E.

(Comparative Example 21)
A toner (T21 ′) was obtained in the same manner as in Example 19 except that the toner binder A was changed to the toner binder E.

(Comparative Example 22)
A toner (T22 ′) was obtained in the same manner as in Example 20 except that the toner binder A was changed to the toner binder E.

(Comparative Example 23)
A toner (T23 ′) was obtained in the same manner as in Example 21 except that the toner binder A was changed to the toner binder E.

(Comparative Example 24)
A toner (T24 ′) was obtained in the same manner as in Example 22 except that the toner binder A was changed to the toner binder E.

[Evaluation method (positively charged toner)]
(Evaluation item)
(1) Low temperature fixability (tape peelability)
4 parts by weight of toner and 96 parts by weight of a silicone-coated ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size 100 μm) were mixed for 5 minutes with a tumbler mixer to obtain a developer. Next, a developer is mounted on an apparatus in which the copier imagio 105 (manufactured by Ricoh) is modified so that fixing can be performed outside the apparatus, and the toner adhesion amount is adjusted to 0.5 mg / cm ² , and 2 cm × 12 cm. An unfixed image was obtained. Further, while fixing the fixing roll temperature from 100 ° C. to 250 ° C. in increments of 5 ° C., the unfixed image was fixed at a linear speed of 1500 mm / second, and a fixing test was conducted. “RICOPY PPC paper TYPE6000” (manufactured by Ricoh) was used as the fixing paper.
A scotch tape (Sumitomo 3M Co., Ltd.) is applied to the image obtained at each fixing temperature, and after leaving for 3 hours, the tape is peeled off and transferred to a white paper. The density of the unfixed image adhering to the tape is determined by X-Rite 938 (manufactured by X-Rite). ), And the difference from the blank of 0.150 or more was evaluated as unfixed. First, the temperature of the fixing roller exceeding 0.150 was set as the minimum fixing temperature, and the low-temperature fixing property was evaluated according to the following evaluation criteria. .
[Evaluation criteria]
A: Minimum fixing temperature is less than 140 ° C. ○: Minimum fixing temperature is 140 ° C. or higher and lower than 150 ° C. ×: Minimum fixing temperature is 150 ° C. or higher

(2) Evaluation of soiling property As in (1), the toner produced in Examples and Comparative Examples was developed on a solid sheet of 10,000 sheets with a copying machine under high temperature and high humidity, and then the scotch tape ( Sumitomo 3M Co., Ltd.) is peeled off, the tape is peeled off, transferred to a blank sheet, and the background stain density adhering to the tape is measured with X-Rite 938 (manufactured by X-Rite Co., Ltd.). The soil resistance was evaluated as occurrence, and the soil resistance was good when it was less than 0.010 and less than 0.005, and the soil resistance was very good when it was less than 0.005.
[Evaluation criteria]
◎: Soil stain resistance is very good. ○: Soil stain resistance is good.

[Evaluation method (negatively charged toner)]
(Evaluation item)
(1) Low temperature fixability (tape peelability)
A developer was obtained by mixing 4 parts by weight of toner and 96 parts of a ferrite carrier (F-150, manufactured by Powdertech) for 5 minutes using a tumbler mixer. Next, a developer is mounted on an apparatus in which the copier imagio Neo C385 (manufactured by Ricoh) is modified so that fixing can be performed outside the apparatus, and the toner adhesion amount is adjusted to 0.5 mg / cm ² to 2 cm. A x12 cm unfixed image was obtained. Further, while fixing the fixing roll temperature from 100 ° C. to 250 ° C. in increments of 5 ° C., the unfixed image was fixed at a linear speed of 1500 mm / second, and a fixing test was conducted. “RICOPY PPC paper TYPE6000” (manufactured by Ricoh) was used as the fixing paper.
A scotch tape (Sumitomo 3M Co., Ltd.) is applied to the image obtained at each fixing temperature, and after leaving for 3 hours, the tape is peeled off and transferred to a white paper. ), And the difference from the blank of 0.150 or more was evaluated as unfixed. First, the temperature of the fixing roller exceeding 0.150 was set as the minimum fixing temperature, and the low-temperature fixing property was evaluated according to the following evaluation criteria. .
[Evaluation criteria]
A: Minimum fixing temperature is less than 140 ° C. ○: Minimum fixing temperature is 140 ° C. or higher and lower than 150 ° C. ×: Minimum fixing temperature is 150 ° C. or higher

(2) Evaluation of soiling property As in (1), the toner produced in Examples and Comparative Examples was developed on a solid sheet of 10,000 sheets with a copying machine under high temperature and high humidity, and then the scotch tape ( Sumitomo 3M Co., Ltd.) is peeled off, the tape is peeled off, transferred to a blank sheet, and the background stain density adhering to the tape is measured with X-Rite 938 (manufactured by X-Rite Co., Ltd.). The soil resistance was evaluated as occurrence, and the soil resistance was good when it was less than 0.010 and less than 0.005, and the soil resistance was very good when it was less than 0.005.
[Evaluation criteria]
◎: Soil stain resistance is very good. ○: Soil stain resistance is good.

  It can be seen that the toner of the present invention has good low-temperature fixability and no toner smears even under high temperature and high humidity.

[III] Examples 73 to 74 and Comparative Example 25
(Binder resin synthesis example)
Synthesis example 1
[Synthesis of linear polyester resin]
In a reactor equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 430 parts of PO2 molar adduct of bisphenol A, 300 parts of PO3 molar adduct of bisphenol A, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 parts of acid and 2 parts of titanium dihydroxybis (triethanolaminate) were added as a condensation catalyst, and the reaction was carried out for 10 hours while distilling off the water produced at 220 ° C. under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and when the acid value became 5, it took out, cooled to room temperature, and grind | pulverized, and the linear polyester resin (AX1-1) was obtained.

[Synthesis of non-linear polyester resin]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 350 parts of EO2 molar adduct of bisphenol A, 326 parts of PO3 molar adduct of bisphenol A, 278 parts of terephthalic acid, 40 parts of phthalic anhydride and condensation As a catalyst, 2 parts of titanium dihydroxybis (triethanolaminate) was added and reacted at 230 ° C. for 10 hours while distilling off the water produced in a nitrogen stream. Next, the reaction is carried out under reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 62 parts of trimellitic anhydride, taken out after reaction for 2 hours under sealed at normal pressure, and cooled to room temperature. To obtain a non-linear polyester resin (AX2-1).

[Synthesis of Toner Binder Resin (TB1)]
400 parts of polyester (AX1-1) and 600 parts of polyester (AX2-1) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. for 4 minutes using a steel belt cooler and then pulverized to obtain a toner binder resin (TB1) of the present invention.
The resulting toner binder resin (TB1) has a molecular weight of 5 × 10 ² or less, a content of 3.5%, a molecular weight main peak of 7.5 × 10 ³ , a Tg of 62 ° C., an Mw / Mn ratio of 5.1, and an acid value of 2.3 KOHmg. / G, apparent viscosity measured by a flow tester was 10 ³ Pa · s, and the temperature was 112 ° C. Moreover, THF insoluble matter was not contained.

Synthesis example 2
[Synthesis of linear polyester resin]
A linear polyester resin (AX1-2) was obtained by reacting in the same manner as (AX1-1) in Synthesis Example 1 except that the polycondensation catalyst was replaced with titanylbis (triethanolaminate), cooling to room temperature, and pulverizing.

[Synthesis of non-linear polyester resin]
A linear polyester resin (AX2-2) was obtained by reacting in the same manner as (AX2-1) in Synthesis Example 1 except that the polycondensation catalyst was replaced with titanylbis (triethanolaminate), cooling to room temperature, and pulverizing.

[Synthesis of Toner Binder Resin (TB2)]
500 parts of polyester (AX1-2) and 500 parts of polyester (AX2-2) were powder-mixed for 5 minutes with a Henschel mixer to obtain a toner binder resin (TB2) of the present invention.
The toner binder resin (TB2) obtained has a molecular weight of 5 × 10 ² or less, 3.0%, a molecular weight main peak of 8 × 10 ³ , a Tg of 62 ° C., an Mw / Mn ratio of 4.7, and an acid value of 0.5 KOH mg / g. The apparent viscosity by a flow tester was 10 ³ Pa · s, and the temperature was 116 ° C. Moreover, THF insoluble matter was not contained.

Synthesis example 3
[Synthesis of linear polyester resin for comparison]
The reaction was conducted in the same manner as in (AX1-1) of Synthesis Example 1 except that the polycondensation catalyst was replaced with titanium tetraisopropoxide. Since the reaction was stopped in the middle due to catalyst deactivation and the problem that the generated water could not be distilled occurred, 2 parts of titanium tetraisopropoxide was added four times during the reaction, and a comparative linear polyester resin (CAX1) was added. -1) was obtained.

[Synthesis of non-linear polyester resin for comparison]
The reaction was conducted in the same manner as in (AX2-1) of Synthesis Example 1 except that the polycondensation catalyst was replaced with titanium tetraisopropoxide. The reaction was allowed to proceed for 16 hours under normal pressure and for 8 hours under reduced pressure. Since the reaction rate was slow, 2 parts of titanium tetrapropoxide were added three times during the reaction to obtain a comparative non-linear polyester resin (CAX2-1).

[Synthesis of Comparative Toner Binder Resin (CTB1)]
400 parts of polyester (CAX1-1) and 600 parts of polyester (CAX2-1) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. over 4 minutes using a steel belt cooler and then pulverized to obtain a comparative toner binder resin (CTB1). (CTB1) was a strong purple-brown resin.
The obtained toner binder resin (CTB1) has a molecular weight of 5 × 10 ² or less, 5.1%, a molecular weight main peak of 9.2 × 10 ³ , a Tg of 71 ° C., an Mw / Mn ratio of 4.6, and an acid value of 10.0 KOHmg. / G, apparent viscosity by a flow tester was 10 ³ Pa · s, and the temperature was 117 ° C. Moreover, THF insoluble matter was not contained. This was used as a toner binder (CTB1).

Synthesis example 4
[Synthesis of modified polyester resin]
549 parts of bisphenol A propylene oxide 2 mol adduct, 20 parts of bisphenol A propylene oxide 3 mol adduct, 133 parts of bisphenol A ethylene oxide 2 mol adduct in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe , 10 parts of an ethylene oxide 5 mol adduct of phenol novolac (average polymerization degree of about 5), 252 parts of terephthalic acid, 19 parts of isophthalic acid, 10 parts of trimellitic anhydride and 2 parts of titanium dihydroxybis (diethanolamate) as a condensation catalyst The reaction was carried out for 10 hours at 230 ° C. while distilling off the water produced under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and it was made to react until an acid value became 2 or less. Next, 50 parts of trimellitic anhydride was added and reacted at normal pressure for 1 hour. After reacting under reduced pressure of 20 to 40 mmHg and the softening point reached 105 ° C., 20 parts of bisphenol A diglycidyl ether was added, After taking out at a softening point of 150 ° C., cooling to room temperature, and pulverizing, a modified polyester resin (AY1-1) was obtained.
(AY1-1) molecular weight 5 × 10 ² or less content 2.8%, molecular weight main peak 6.9 × 10 ³ , Tg 64 ° C., Mw / Mn ratio 5.5, acid value 8.1 KOH mg / g, flow The apparent viscosity by a tester was 10 ³ Pa · s, the temperature was 102 ° C., and no THF-insoluble matter was contained. This was used as a toner binder resin (TB3).

Synthesis example 5
[Synthesis of modified polyester resin for comparison]
A modified polyester resin for comparison (CAY1-2) was obtained by reacting in the same manner as in Synthesis Example 4 except that the polycondensation catalyst was replaced with titanium tetrabutoxide.
(CAY1-2) molecular weight 5 × 10 ² or less content 6.1%, molecular weight main peak 10.7 × 10 ³ , Tg 74 ° C., Mw / Mn ratio 7.2, acid value 10.6 KOHmg / g, flow The apparent viscosity by a tester was 10 ³ Pa · s, the temperature was 122 ° C., and the THF-insoluble content was 12%. This was used as a toner binder resin (CTB2).

(Synthesis example of resin charge control agent)
Synthesis example 1
350 parts of 3,4-dichlorophenylmaleimide and 100 parts of 2-acrylamido-2-methylpropanesulfonic acid were copolymerized at a boiling point in dimethylformaldehyde (DMF) for 8 hours using di-t-butyl peroxide as an initiator. Next, 500 parts of n-butyl acrylate and 50 parts of styrene were added, and after graft polymerization for 4 hours using di-t-butyl peroxide as an initiator, DMF was removed by drying under reduced pressure, and volume resistance was 10.5 LogΩ · cm. A resin charge control agent 1 having a weight average molecular weight of 1 × 10 ⁴ , a temperature at which the apparent viscosity becomes 10 ⁴ Pa · s is 96 ° C., and the content of the weight average molecular weight is 1 × 10 ³ or less is 6%.

Synthesis example 2
600 parts of m-nitrophenylmaleimide and 100 parts of perfluorooctane sulfonic acid were copolymerized for 8 hours with di-t-butyl peroxide as an initiator at the boiling point in DMF. Next, 250 parts of 2-ethylhexyl acrylate and 30 parts of styrene were added, and after graft polymerization with di-t-butyl peroxide as an initiator for 4 hours, DMF was removed by drying under reduced pressure, and the volume resistance was 9.5 LogΩ · cm. A resin charge control agent 2 having a weight average molecular weight of 5.5 × 10 ³ , a temperature at which the apparent viscosity becomes 10 ⁴ Pa · s is 85 ° C., and the content of the weight average molecular weight is 1 × 10 ³ or less is 8%.

Synthesis example 3
500 parts of 3,4-dichlorophenylmaleimide and 150 parts of 2-acrylamido-2-methylpropanesulfonic acid were copolymerized at a boiling point in DMF for 8 hours using di-t-butyl peroxide as an initiator. Next, 350 parts of n-butyl acrylate and 250 parts of α-methylstyrene were added, and after graft polymerization for 4 hours using di-t-butyl peroxide as an initiator, DMF was removed by drying under reduced pressure to give a volume resistance of 11 Resin charge control agent having a content of 5 LogΩ · cm, a weight average molecular weight of 9.6 × 10 ⁴ , a temperature at which the apparent viscosity is 10 ⁴ Pa · s is 110 ° C., and a weight average molecular weight of 1 × 10 ³ or less is 5%. 3 was obtained.

Synthesis example 4
400 parts of 3,4-dichlorophenylmaleimide and 200 parts of perfluorooctane sulfonic acid were copolymerized for 8 hours with di-t-butyl peroxide as an initiator at the boiling point in DMF. Next, 300 parts of n-butyl acrylate was added, and graft polymerization was carried out for 4 hours using di-t-butyl peroxide as an initiator. Then, DMF was removed by drying under reduced pressure, volume resistance 10.4 LogΩ · cm, weight number average molecular weight. A resin charge control agent 4 having a temperature of 1.5 × 10 ⁴ , an apparent viscosity of 10 ⁴ Pa · s at 105 ° C., and a content of 6% having a weight average molecular weight of 1 × 10 ³ or less was obtained.

Synthesis example 5
400 parts of 3,4-dichlorophenylmaleimide and 100 parts of 2-acrylamido-2-methylpropanesulfonic acid were copolymerized at a boiling point in DMF for 8 hours using di-t-butyl peroxide as an initiator. Next, 500 parts of n-butyl acrylate and 100 parts of styrene were added and dissolved. After graft polymerization with di-t-butyl peroxide as an initiator for 4 hours, DMF was removed by drying under reduced pressure, and the volume resistance was 9.3 LogΩ. A resin charge control agent 5 having a content of 6% in terms of cm, a weight average molecular weight of 3 × 10 ⁴ , a temperature at which the apparent viscosity becomes 10 ⁴ Pa · s is 101 ° C., and the weight average molecular weight is 1 × 10 ³ or less was obtained.

<Example 73>
The colorant was processed according to the following formulation.
Yellow colorant formulation:
Binder resin TB1 100 parts by weight C.I. I. Pigment Yellow 180 100 parts by weight Red colorant formulation:
Binder resin TB1 100 parts by weight C.I. I. Pigment Red 122 100 parts by weight Blue colorant formulation:
Binder resin TB1 100 parts by weight C.I. I. Pigment Blue 15.3 100 parts by weight Black colorant formulation:
Binder resin TB1 100 parts by weight Carbon black 100 parts by weight

  For each color, the above materials were put into a Henschel mixer and mixed, and then the mixture was put into an air-cooled two-roll mill and melted and kneaded for 15 minutes. Thereafter, the kneaded product was rolled and cooled, and coarsely pulverized with a hammer mill to obtain a binder resin-treated coloring material.

Next, a toner was prepared according to the following formulation.
Yellow toner prescription:
Binder resin TB1 91 parts by weight Binder resin TB1 treated yellow colorant 12 parts by weight Resin charge control agent 1 3 parts by weight Magenta toner formulation:
Binder resin TB1 92 parts by weight Binder resin TB1 treated red colorant 10 parts by weight Resin charge control agent 1 3 parts by weight Cyan toner formulation:
Binder resin TB1 94 parts by weight Binder resin TB1 treated blue colorant 6 parts by weight Resin charge control agent 1 3 parts by weight Black toner formulation:
Binder resin TB1 90 parts by weight Binder resin TB1 treated black colorant 12 parts by weight Binder resin TB1 treated blue colorant 2 parts by weight Resin charge control agent 1 3 parts by weight

The above materials were mixed for each color in a Henschel mixer, and the resulting mixture was put into a roll mill heated to 110 ° C. and melted and kneaded for 30 minutes. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an air jet mill. Further, fine powder was removed by an air classifier to obtain each color toner. The T1 / T2 of the binder resin TB1 and the resin charge control agent 1 was 1.16.
The following additives were mixed in a Henschel mixer with respect to 100 parts by weight of the obtained color toners to form a one-component developer.
Hydrophobic silica (primary particle size; 0.02 μm) 2.5 parts by weight Hydrophobic titanium oxide (primary particle size; 0.015 μm, specific surface area: 90 mg / cm ² )
0.8 parts by weight

  The obtained one-component developer was set in a commercially available digital full-color printer (IPSiOColor 6500 manufactured by Ricoh) to form an image. The obtained image was clear and no abnormalities such as background stains were observed. When the developing roller was visually observed, the toner thin layer on the roller was uniform. The amount of charge on the developing roller was measured by a suction method. As a result, the yellow developer was −35 μC / g, the magenta developer was −30 μC / g, the cyan developer was −31 μC / g, and the black developer was −32 μC / g. there were. Images were similarly formed under high temperature and high humidity conditions of 27 ° C. and 80% RH, and low temperature and low humidity conditions of 10 ° C. and 15% RH, but no change was observed, and a good image was formed. When a durability test was performed up to a total of 40,000 full-color images in each environment continuously at room temperature, low temperature and low humidity, high temperature and high humidity, and normal temperature, no significant change was observed in the fixed image. The image was clear with no background stains. Visual observation of the developing roller revealed no significant change in the toner thin layer on the roller. At this time, the developer charge amount was yellow developer-31 μC / g, magenta developer-29 μC / g, cyan development. Agent-29 μC / g and black developer-27 μC / g. The developing roller, blade, and photoreceptor were visually observed, but no filming was observed.

<Example 74>
The colorant was processed according to the following formulation.
Yellow colorant formulation:
Binder resin TB2 100 parts by weight C.I. I. Pigment Yellow 180 100 parts by weight Red colorant formulation:
Binder resin TB2 100 parts by weight C.I. I. Pigment Red 146 100 parts by weight Blue colorant formulation:
Binder resin TB3 100 parts by weight C.I. I. Pigment Blue 15.3 100 parts by weight Black colorant formulation:
Binder resin TB3 100 parts by weight Carbon black 100 parts by weight

  For each color, the above materials were put into a Henschel mixer and mixed, and then the mixture was put into an air-cooled two-roll mill and melted and kneaded for 15 minutes. Thereafter, the kneaded product was rolled and cooled, and coarsely pulverized with a hammer mill to obtain a binder resin-treated coloring material.

Next, a toner was prepared according to the following formulation.
Yellow toner prescription:
Binder resin TB2 91 parts by weight Binder resin TB2 treated yellow colorant 12 parts by weight Resin charge control agent 2 3 parts by weight Magenta toner formulation:
Binder resin TB2 92 parts by weight Binder resin TB2 treated red colorant 10 parts by weight Resin charge control agent 2 3 parts by weight Cyan toner formulation:
Binder resin TB3 94 parts by weight Binder resin TB3 treated blue colorant 6 parts by weight Resin charge control agent 3 3 parts by weight Black toner formulation:
Binder resin TB3 90 parts by weight Binder resin TB3 resin-treated black colorant 12 parts by weight Binder resin TB3 resin-treated blue colorant 2 parts by weight Resin charge control agent 4 3 parts by weight

The above materials were mixed in a Henschel mixer for each color, and the resulting mixture was put into a biaxial continuous kneader heated to 80 ° C. and melt-kneaded. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an airflow pulverizer. Further, fine powder was removed by an air classifier to obtain each color toner. T1 / T2 of the binder resin TB2 and the resin charge control agent 2 is 1.11, T1 / T2 of the binder resin TB3 and the resin charge control agent 3 is 1.15, and T1 / T2 of the binder resin TB3 and the resin charge control agent 4 Was 1.21. The following additives were mixed with 100 parts by weight of each color toner using a Henschel mixer.
-Hydrophobic silica (primary particle size; 0.02 µm) 2.1 parts by weight-Hydrophobic titanium oxide (primary particle size: 0.015 µm, specific surface area: 120 mg / cm ² )
1.0 part by weight

  6 parts by weight of the obtained toner and 94 parts of a silicone resin coated carrier were mixed to obtain a two-component developer. The obtained two-component developer was set in a commercially available digital full-color printer (IPSiOColor 7100 manufactured by Ricoh) to form an image. The obtained image was clear with no background stains. No abnormalities were observed in image and charging at high temperature and high humidity and low temperature and low humidity. Even when a durability test of up to 10,000 sheets with a full-color image was performed, no abnormal image was observed, and the inside of the apparatus was observed after the test, but no scattering was observed, and there was no adhesion to the photoreceptor.

<Comparative Example 25>
The colorant was processed according to the following formulation.
Yellow colorant formulation:
Binder resin CTB1 100 parts by weight C.I. I. Pigment Yellow 180 100 parts by weight Red colorant formulation:
Binder resin CTB1 100 parts by weight C.I. I. Pigment Red 122 100 parts by weight Blue colorant formulation:
Binder resin CTB2 100 parts by weight C.I. I. Pigment Blue 15.3 100 parts by weight Black colorant formulation:
Binder resin CTB2 100 parts by weight Carbon black 100 parts by weight

  For each color, the above materials were put into a Henschel mixer and mixed, and then the mixture was put into an air-cooled two-roll mill and melted and kneaded for 15 minutes. Thereafter, the kneaded product was rolled and cooled, and coarsely pulverized with a hammer mill to obtain a binder resin-treated coloring material.

Next, a toner was prepared according to the following formulation.
Yellow toner formulation;
Binder resin CTB1 91 parts by weight Binder resin CTB1 treated yellow colorant 12 parts by weight Resin charge control agent 1 3 parts by weight Magenta toner formulation:
Binder resin CTB1 92 parts by weight Binder resin CTB1 treated red colorant 10 parts by weight Resin charge control agent 3 3 parts by weight Cyan toner formulation:
Binder resin CTB2 94 parts by weight Binder resin CTB2 treated blue colorant 6 parts by weight Resin charge control agent 5 3 parts by weight Black toner formulation:
Binder resin CTB2 90 parts by weight Binder resin CTB2 treated black colorant 12 parts by weight Binder resin CTB2 treated blue colorant 2 parts by weight Resin charge control agent 5 3 parts by weight

The above materials were mixed in a Henschel mixer for each color, and the resulting mixture was placed in a roll mill heated to 100 ° C., and melted and kneaded for 20 minutes. Thereafter, the kneaded product was cooled, coarsely pulverized with a hammer mill, and finely pulverized with an air jet mill. Further, fine powder was removed by an air classifier to obtain each color toner. T1 / T2 of the binder resin CTB1 and the resin charge control agent 1 is 1.20, T1 / T2 of the binder resin CTB1 and the resin charge control agent 3 is 1.11, and T1 / T2 of the binder resin CTB2 and the resin charge control agent 5 Was 1.34.
The following additives were mixed in a Henschel mixer with respect to 100 parts by weight of the obtained color toners to form a one-component developer.
Hydrophobic silica (primary particle size; 0.02 μm) 2.5 parts by weight Hydrophobic titanium oxide (primary particle size; 0.015 μm, specific surface area: 90 mg / cm ² )
0.8 parts by weight

  The obtained one-component developer was set in a commercially available digital full-color printer (IPSiOColor 6500 manufactured by Ricoh) to form an image. The obtained image was clear and no abnormalities such as background stains were observed. When the developing roller was visually observed, the toner thin layer on the roller was uniform. The amount of charge on the developing roller was measured by a suction method. As a result, the yellow developer was −43 μC / g, the magenta developer was −36 μC / g, the cyan developer was −38 μC / g, and the black developer was −35 μC / g. there were. When an image was formed under high-temperature and high-humidity conditions of 27 ° C. and 80% RH, the image was blurred. Further, when the same image was formed under a low temperature and low humidity condition of 10 ° C. and 15% RH, a faint image having a low ID was obtained. When a durability test using full-color images was performed under normal conditions at room temperature, low temperature and low humidity, high temperature and high humidity, and normal temperature, abnormalities such as background stains, dust, and streaks occurred on the images. When the developing roller was visually observed at this time, streaks were generated in the circumferential direction in the toner thin layer on the roller. When the charge amount of the developer was measured, it was deteriorated to be yellow developer-28 μC / g, magenta developer-22 μC / g, cyan developer-25 μC / g, and black developer-21 μC / g.

  The toner binder of the present invention and the toner of the present invention containing the same are excellent in both blocking resistance, stain resistance and low-temperature fixability of the toner under high temperature and high humidity, and in a high temperature and high humidity environment or at a low temperature. No matter how low-humidity environment or high-image area output is used over time, there is no problem of high-quality images, that is, there is no problem such as the toner component sticking to the carrier or the developing sleeve and reducing the charging ability of the developer. It is useful as a toner for developing an electrostatic image.

1 is a schematic configuration diagram of a developing device of an image forming apparatus in the present invention. FIG. 4 is a diagram schematically illustrating the shape of a toner in order to explain the shape factor SF-1 and the shape factor SF-2. FIG. 4 is a diagram schematically illustrating the shape of a toner in order to explain the shape factor SF-1 and the shape factor SF-2. It is a figure showing another example of the apparatus structure of the image forming apparatus in this invention. It is a figure showing another example of the apparatus structure of the image forming apparatus in this invention. 1 is a schematic diagram illustrating a part of a configuration of an image forming apparatus using a contact-type charging device according to the present invention. 1 is a schematic diagram showing a configuration of a tandem color image forming apparatus of the present invention. 1 is a schematic diagram illustrating a configuration of an image forming apparatus having an intermediate transfer member, which is a tandem color image forming apparatus of the present invention. 1 is a schematic diagram illustrating an overall configuration of an image forming apparatus of a tandem type indirect transfer system according to the present invention. 1 is a schematic diagram illustrating a configuration of a tandem indirect transfer type image forming apparatus including a process cartridge of the present invention.

Explanation of symbols

(Figure 1)
DESCRIPTION OF SYMBOLS 1 Developing apparatus 2 Toner hopper 3 Toner flow apparatus 4 Developer accommodating part 5 1st stirring screw 6 2nd stirring screw 7 Developing sleeve 8 Photoconductor 9 Doctor 10 Power supply 23 Toner supply port (FIGS. 4 and 5)
DESCRIPTION OF SYMBOLS 10 Photoconductor 20 Charging roller 30 Exposure apparatus 40 Developing apparatus 41 Developing belt 42 Developing tank 43 Pumping roller 44 Coating roller 45 Developing unit 50 Intermediate transfer body 51 Suspension roller 52 Corona charger 60 Cleaning device 70 Gradual electric lamp 80 Transfer roller 90 Cleaning Device 100 Transfer paper (Fig. 6)
140 Photosensitive member 160 Charging roller (FIGS. 7 and 8)
DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Transfer apparatus, Primary transfer apparatus 3 Sheet conveyance belt 4 Intermediate transfer body 5 Secondary transfer apparatus 6 Paper feed apparatus 7 Fixing apparatus 8 Photoconductor cleaning apparatus 9 Intermediate transfer body cleaning apparatus (FIG. 9)
DESCRIPTION OF SYMBOLS 10 Intermediate transfer body 14, 15, 16 Support roller 17 Intermediate transfer body cleaning apparatus 18 Image forming means 20 Tandem image forming apparatus 21 Exposure apparatus 22 Secondary transfer apparatus (transfer roller)
23 roller 24 secondary transfer belt 25 fixing device 25a fixing heater 25b driven roller 25c driving roller 25d fixing temperature sensor 25e flat substrate 26 fixing belt (fixing film)
27 Pressure roller 28 Sheet reversing device 30 Document table 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Photoconductor 41 Developing belt 42 Paper feed roller 43 Paper bank 44 Paper feed cassette 45 Separation Rollers 46 and 48 Paper feed path 47 Transport roller 49 Registration roller 50 Paper feed roller 51 Manual feed tray 52 Separating roller 53 Manual feed path 55 Switching claw 56 Discharge roller 57 Paper discharge tray 60 Charging device 60a Charging roller 60b Brush roller 60c Core metal 60d Conductive rubber layer 60e Brush portion 60f Power supply 61 Developing device 62 Primary transfer device 63 Cleaning device 64 Static elimination device (static elimination lamp)
100 Copier body 200 Paper feed table 300 Scanner 400 Automatic document feeder

Claims (51)

In the method for producing an electrostatic charge image developing toner containing at least a colorant and a binder resin, the toner has a volume average particle diameter of 2.0 to 10.0 μm, a volume average particle diameter (Dv) and a number average particle diameter. The ratio (Dv / Dn) to (Dn) is in the range of 1.00 to 1.40, and the binder resin contains at least a polycondensation polyester resin. The polyester resin is treated with titanium dihydroxybis. A method for producing a toner for developing an electrostatic charge image, wherein the toner is formed in the presence of (triethanolaminate ) .
2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the polyester resin contains at least one kind of resin at least a part of which is modified with polyepoxide (c). The polyester resin does not contain a THF-insoluble component, and in the molecular weight distribution in gel permeation chromatography, the content ratio of the component having a molecular weight of 5 × 10 ² or less is 4% by weight or less, and the weight molecular weight is 3 × 10 ^{3 to} 9 ×. method for producing a toner according to claim 1 or 2, characterized in that the 10 ^third region and has a main peak. Method for producing a toner according to any one of claims 1 to 3 endothermic peak in DSC of the binder resin is characterized in that in the range of 60 to 70 ° C.. The weight average molecular weight of the binder resin (Mw) to number-average molecular weight (Mn) of the electrostatic image developing according to any ratio of claims 1 to 4, characterized in that a 2 ≦ Mw / Mn ≦ 10 of Toner manufacturing method . Method for producing a toner according to any one of claims 1 to 5, wherein the acid value of the binder resin is not more than 10 KOH mg / g. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 6 , wherein a temperature at which an apparent viscosity of the binder resin by a flow tester becomes 10 ³ Pa · s is 95 to 120 ° C. . The toner manufacturing method of the electrostatic image developing toner according to any one of claims 1 to 7, characterized in that it contains a charge control agent. 9. The method for producing a toner for developing an electrostatic charge image according to claim 8 , wherein the charge control agent is represented by the following general formula (III).

9. The method for producing a toner for developing an electrostatic charge image according to claim 8 , wherein the charge control agent is represented by the following general formula (IV).

9. The electrostatic image developing toner according to claim 8 , wherein the charge control agent is bis [1- (5-chloro-2-hydroxyphenylazo) -2-naphtholato] chromium (III) acid. Manufacturing method . The method for producing a toner for developing an electrostatic charge image according to claim 8 , wherein the charge control agent is nigrosine. 9. The method for producing a toner for developing an electrostatic image according to claim 8 , wherein the charge control agent is represented by the following general formula (V).

9. The method for producing a toner for developing an electrostatic charge image according to claim 8 , wherein the charge control agent is perfluoroalkyltrimethylammonium iodide. The charge controlling agent, the repeating unit is 65 to 97 wt% of the following general formula (VI), and the repeating unit represented by the following general formula (VII) is from 3 to 35 wt%, and the weight average molecular weight The method for producing a toner for developing an electrostatic charge image according to claim 8 , wherein the toner is a quaternary ammonium base-containing copolymer in the range of 2000 to 10,000.

(R ₁ is a hydrogen atom or a methyl group, R ₂ is a hydrogen atom or a methyl group, R ₃ is an alkylene group, and R ₄ , R ₅ and R ₆ are each an alkyl group.) The method for producing a toner for developing an electrostatic charge image according to claim 8 , wherein the charge control agent is represented by the following general formula (VIII).

The method for producing a toner for developing an electrostatic charge image according to claim 8 , wherein the charge control agent is represented by the following general formula (IX).

(Wherein, a ₁ is 0.8 to 0.98, b ₁ is 0.01 to 0.19, c ₁ is 0.01 to 0.19, and a ₁ + b ₁ + c ₁ is 1) The method for producing a toner for developing an electrostatic charge image according to claim 8 , wherein the charge control agent comprises two or more kinds according to any one of claims 9 to 17 . 19. The method for producing a toner for developing an electrostatic charge image according to claim 9 , wherein the charge control agent is contained in a toner base in an amount of 0.1 to 15.0% by weight. The charge control agent comprises a resin charge control agent, and the resin charge control agent is at least (1) a sulfonate group-containing monomer, (2) an aromatic monomer having an electron withdrawing group, and (3) an acrylic ester. Among the monomers and / or methacrylic acid ester monomers and (4) aromatic vinyl monomers, (1) to (3) or (1) to (4) are structural units, and the volume resistance of the resin charge control agent is 9 The electrostatic charge according to claim 8 , wherein the content ratio of the component having a weight average molecular weight of 1 × 10 ³ or less in the resin charge control agent is 10% by weight or less. A method for producing a toner for image development. (1) The repeating unit of the sulfonic acid group-containing monomer of the resin charge control agent is 1 to 30% by weight with respect to the weight of the resin charge control agent, The repeating unit is 1 to 80% by weight based on the weight of the resin charge control agent, and the repeating unit of (3) acrylate ester monomer and / or methacrylic acid ester monomer of the resin charge control agent is based on the weight of the resin charge control agent 10 to 80 wt%, to claim 20, wherein the resin charge control agent (4) an aromatic vinyl monomer repeating units of is contained in a proportion of 0-30% by weight relative to the resin charge controlling agent by weight A method for producing the toner for developing an electrostatic image according to claim 1. Aromatic monomers having (2) an electron-withdrawing group of the resin charge controlling agent has been replaced by a chlorine atom or a nitro group, according to claim 20 or, wherein the phenyl maleimide substituents or phenyl itaconic imide substitutions 21. A method for producing a toner for developing an electrostatic charge image according to any one of 21 . 23. The dry electrostatic charge image developing toner according to claim 20 , wherein a temperature at which an apparent viscosity of the resin charge control agent by a flow tester is 10 ⁴ Pa · s is 85 to 110 ° C. Manufacturing method . 24. The method for producing a toner for developing an electrostatic charge image according to claim 20, wherein the resin charge control agent has a weight average molecular weight of 5 × 10 ³ to 1 × 10 ⁵ . When the temperature at which the apparent viscosity by the flow tester of the binder resin is 10 ³ Pa · s is T1, and the temperature at which the apparent viscosity by the flow tester of the resin charge control agent is 10 ⁴ Pa · s is T2, T1 and T2 25. The method for producing a toner for developing an electrostatic charge image according to claim 20 , wherein a relationship of 0.9 <T1 / T2 <1.4 is satisfied. The method for producing a toner for developing an electrostatic charge image according to any one of claims 20 to 25 , wherein the resin charge control agent is contained in an amount of 0.1 to 20% by weight based on toner particles. In the toner, the following fines content 4μm is 0-20% by number, coarse powder content of not less than 12.7μm is in any one of claims 1 to 26, characterized in that 0 to 3% by number A method for producing the toner for developing an electrostatic image according to claim 1. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 27 , wherein the toner has an average circularity of 0.91 or more and less than 1.00. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 28 , wherein the toner has an average circularity of 0.94 or more and less than 1.00. The toner, a SF-1 of 100 to 180, SF-2 is for developing an electrostatic charge image according to any one of claims 1 to 29, characterized in that a toner in the range of 100 to 180 Toner manufacturing method . The toner manufacturing method of the electrostatic image developing toner according to any one of claims 1 to 30, characterized in that cohesion is 1 to 25 (%). The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 31 , wherein the toner has a loose apparent density of 0.2 to 0.7 (g / ml). The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 32 , wherein the toner has a volume resistivity of 8 to 15 (Ω · cm). The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 33 , wherein the toner has a softening point of 80 to 180 ° C. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 34 , wherein the toner has a glass transition temperature Tg of 35 to 90 ° C. 36. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 35 , further comprising one or more additives selected from a release agent and a fluidizing agent. 37. The method for producing a toner for developing an electrostatic charge image according to claim 36 , wherein the releasing agent is a wax having a hydrocarbon straight chain. The toner manufacturing method of the electrostatic image developing toner according to any one of claims 1 to 37, wherein the external additive is one that was dry-mixed with the mixed medium. 38. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 37 , wherein the toner is obtained by wet-mixing an external additive. 40. The method for producing a toner for developing an electrostatic charge image according to claim 38 or 39 , wherein the external additive contains at least one selected from a metal oxide, a metal nitride, and a metal carbide. 41. The method for producing a toner for developing an electrostatic charge image according to any one of claims 38 to 40 , wherein the external additive contains at least primary particles of silica having a number average particle diameter of 3 to 200 nm. 41. The method for producing a toner for developing an electrostatic charge image according to claim 38, wherein the external additive includes at least a titanium oxide having a primary particle number average particle diameter of 3 to 200 nm. 41. The electrostatic charge image according to claim 38, wherein the external additive contains at least two types of silica having a number average particle size of primary particles of 3 to 200 nm and titanium oxide of 3 to 200 nm. A method for producing a developing toner. 44. The electrostatic charge image developing toner according to claim 43 , wherein the silica content S (wt%) of the external additive and the titanium oxide content T (wt%) have a relationship of S ≧ T. Manufacturing method . The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 44 , wherein the toner contains at least a fatty acid metal salt. 46. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 45 , wherein the toner is a pulverized toner including at least a pulverizing step. 46. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 45 , wherein the toner is a chemical toner produced through a process in which the toner is dispersed in at least a solvent. . 46. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 45 , wherein the toner is a chemical toner produced in a process including at least a polymerization reaction. In the toner, a toner composition containing at least a polymer having a site capable of reacting with a compound having an active hydrogen group, a polyester resin, a colorant, and a release agent is crosslinked and / or in the presence of resin fine particles in an aqueous medium. method for producing a toner according to any one of claims 1 to 45 or elongation reacted characterized by produced. The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 49 , wherein the toner is a toner used in a color image forming apparatus. The toner manufacturing method of the electrostatic image developing toner according to any one of claims 1 to 50, characterized in that a magnetic toner containing at least a magnetic material.

Images